Polyolefin-based ionomer and preparation thereof

Abstract

Elastomers based on polyolefin ionic polymers and methods for making the same. The ionic polymers can include copolymers comprising: C2-C 60 alpha-olefin monomer units; optionally C2-C 60 alpha-olefin comonomer units; optionally diene units; and about 0.1 wt% to about 20 wt% metal-alkenyl units based on the weight of the copolymer, wherein the metal-alkenyl units have the formula -R(A ‑ ), wherein R is an alkyl group containing 2 to 10 carbon atoms and A ‑ is an anionic group. The copolymers can further comprise one or more metal cations derived from alkali metals, alkaline earth metals, Group 3-12 metals, Group 13-16 metals, and combinations thereof (one or more). The ionic polymers have a glass transition temperature of -60 °C to 5 °C, and a weight average molecular weight (Mw) of 50 to 5,000 kg / mol.

Description

[0001] Inventors: Tzu-Pin Lin, Carlos R. Lopez-Barron, Avery R. Smith, Brian J. Rohde, Alex E. Carpenter, Matthew W. Holtcamp, Jo Ann M. Canich, and John R. Hagadorn

[0002] Cross Reference to Related Applications

[0003] This application claims the benefit of and priority to U.S. Provisional Application No. 63 / 131,505, filed December 29, 2020, the disclosure of which is incorporated by reference herein. TECHNICAL FIELD

[0004] The present disclosure relates to polyolefin-based ionomers and the preparation of polyolefin-based ionomers. The present disclosure also relates to non-supported catalysts for the preparation of elastomeric polyolefin-based ionomers. BACKGROUND

[0005] Cross-linked rubbers are used in many industrial and consumer applications, such as in coatings, seals, tires, tubing, and roofing, among others. Cross-linked rubbers can be composed of vulcanized natural rubber, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, polyisoprene, isoprene-isobutylene copolymer, ethylene-propylene rubber, ethylene propylene diene monomer (EPDM) rubber, silicone elastomers, fluoroelastomers, polyurethane elastomers, and nitrile rubber, among others. Cross-linked rubbers can be advantageous for combining toughness, elasticity, and resistance to heat, chemicals, and other environmental factors. However, cross-linked rubbers also have important drawbacks. For example, cross-linked rubbers cannot flow, even at elevated temperatures, due to their high cross-linking density. Additionally, cross-linked rubbers cannot be reprocessed because their cross-linking is irreversible.

[0006] Accordingly, there is a need to develop alternatives to cross-linked rubbers that can flow and be reprocessed, while also retaining the desirable properties of cross-linked rubbers, such as toughness, elasticity, and resistance to heat, chemicals, and other environmental exposures.

[0007] Additionally, while cross-linked rubbers do have advantageous mechanical properties, such as the ability to elastically deform, these mechanical properties depend on their base polymer composition. For example, in the case of styrene-butadiene copolymers, their elastic properties worsen as the styrene content increases. Additionally, the various properties of cross-linked rubbers can depend to a large extent on their specific degree of cross-linking. However, cross-linking can be problematic because cross-linked rubbers tend to only allow limited adjustment of their degree of cross-linking, such as in the case of EPDM rubbers.

[0008] Accordingly, there remains a need for polymer alternatives to crosslinked rubbers that can maintain the mechanical properties of crosslinked rubbers, such as their ability to elastically deform, without the need to crosslink the polymers.

[0009] According to the references cited in the Information Disclosure Statement pursuant to 37 C.F.R. 1.97(h): U.S. Patent No. 8,329,848; WO Patent Publication Nos. 2017 / 013246; 2010 / 050437; 2019 / 122457; JP Patent Publication Nos. 2011 / 256256; 2007 / 262335; 2007 / 262631; 2007 / 262336; 2007 / 262330; 2007 / 262338; 2007 / 261211; 2007 / 254575; 2006 / 089542; 2003 / 246820; 2005 / 320420; Nam, Y. et al. (2002) “Propene Polymerization with Stereospecific Metallocene Dichloride- [Ph3C][B(C6F5)4] Using ω-Alkenylaluminum as an Alkylation Reagent and as a Functional Comonomer,” Macromolecules, v. 35(18), pp. 6760-6762; Lee, J. et al. (2013) “Copolymerization of norbornene with ω-alkenylaluminum as a precursor comonomer for introduction of carbonyl moieties,” Journal of Polymer Science, Part A: Polymer Chemistry, V. 51(23), pp. 5085-5090; Shiono, T. et al. (2013) “Facile Synthesis of Hydroxy-Functionalized Cycloolefin Copolymer Using ω-Alkenylaluminium as a Comonomer,” Macromol. Chem. Phys., 214(19), pp. 2239-2244; Kang, K. et al. (1998) “Preparations of Propylene and Ethylene Ionomers with Solvay-Type TiCL3 Catalyst,” J.M.S.-Pure Appl. Chem., A35(6), pp. 1003-1016; Landoll, L.Zhou, et al. (1989) "Polypropylene Ionomers," Journal of Polymer Science: Part A: Polymer Chemistry, v. 27, pp. 2189-2201. SUMMARY SUMMARY

[0011] Elastomeric polyolefin-based ionomers and methods for making the same are provided. It has been discovered that the polyolefin-based ionomers provided herein can flow and can be reprocessed while retaining certain properties of crosslinked rubbers, including toughness, elasticity, and resistance to heat, chemicals, and other environmental exposures. The ionomers can include copolymers comprising: C2-C 60 a-olefin monomer units; optionally C2-C 60 a-olefin comonomer units; optionally diene units; and about 0.1 wt% to about 20 wt% metal-alkenyl units, based on the weight of the copolymer, wherein the metal-alkenyl units have the formula— R(A - )—, wherein R is an alkyl group containing 2 to 10 carbon atoms, and A - is an anionic group. The copolymers can further comprise one or more metal cations derived from alkali metals, alkaline earth metals, Group 3-12 metals, Group 13-16 metals, and combinations thereof (one or more). The ionomers have a glass transition temperature of -60 °C to 5 °C, and a weight average molecular weight (Mw) of 50 to 5,000 kg / mol. BRIEF DESCRIPTION OF DRAWINGS

[0012] So that the above-recited features of the present disclosure can be understood in detail, a more particular description can be had by reference to embodiments. Some aspects of the embodiments are shown in the drawings. It is to be noted, however, that the drawings are provided for illustration purposes only and should not be considered to limit the scope of the disclosure in any way. It is being allowed that other equally effective embodiments can be used.

[0013] Figure 1 is a graphical illustration showing the comparison of FTIR analysis between ethylene-propylene-AVTA-K ionomer (Example 1), ethylene-propylene copolymer (Control 1), and potassium acetate standard sample according to at least one embodiment provided herein.

[0014] Figure 2A shows the stress-strain curves of two samples (Example 1 and Control 1) measured at 25 °C according to at least one embodiment provided herein.

[0015] Figure 2Bis a graph illustrating hysteresis testing of an experimental sample of an ethylene-propylene-AVTA-K ionomer (Example 1) measured at 25 °C, in accordance with at least one embodiment provided herein.

[0016] Figure 3 is a graph illustrating a comparison of scattering data between an experimental sample of an ethylene-propylene-AVTA-K ionomer (Example 1) and an ethylene-propylene copolymer (Control 1), in accordance with at least one embodiment provided herein.

[0017] Figure 4 is a DMTA analysis of an experimental sample of an ethylene-propylene-AVTA-K ionomer (Example 2) and an ethylene-propylene copolymer (Control 2), in accordance with at least one embodiment provided herein.

[0018] Figure 5A 、 5B , 5C, 5D, and 5E illustrate thirty-two (32) exemplary catalyst complex represented by Formula (A). DETAILED DESCRIPTION

[0020] The present disclosure relates generally to polyolefin-based ionomers and the preparation of polyolefin-based ionomers. It has been discovered that polyolefins bearing polar ionic groups can have unique and improved properties, such as improved adhesion and printability, compared to non-polar polyolefins. Some types of polar polyolefins can also provide advanced functionalities, including applications in fuel, battery, and sensor materials. Polyolefin-based ionomers (ionomeric polyolefins) are prepared from polymers or copolymers (polymer precursors), including, for example, polyethylene, polypropylene, or copolymers of ethylene and propylene.

[0021] Polyolefin-based ionomers can be difficult to prepare because heteroatom-containing ionic groups, such as hydroxyl or carboxylic acid groups, can poison the catalyst(s) used to form the polymer precursors (of the ionomeric polyolefin). Heteroatoms are atoms other than carbon or hydrogen. In that regard, transition metal catalysts, such as titanium and zirconium metallocenes, can be used to polymerize non-polar olefins because they tend to form polyolefins with high molecular weight and high functional monomer content. However, transition metal catalysts are easily poisoned by heteroatoms. Some polyolefin catalysts are passivated by nucleophilic heteroatoms, making ionomeric polyolefin synthesis challenging. Methods of preparing polyolefin-based ionomers are provided that avoid the interaction between heteroatom-containing ionic groups and metal catalysts. Such methods include ethylene-based addition copolymerization techniques.

[0022] Suitable polyolefin-based polymer precursors can include olefin comonomer units and metal-alkenyl comonomer units, such as vinyl aluminum. In some aspects, the metal-alkenyl units can be or can include vinyl aluminum (AV), such as di(isobutyl)(7-octen-1-yl)aluminum (AVTA-1 / 8). In at least some aspects, the metal-alkenyl units can be used to make polyolefins having pendent metal groups, such as pendent aluminum groups. Thereafter, the pendent metal groups can be converted to ionic groups via oxidation. Thereafter, the polyolefin-based polymer precursors can undergo ion exchange with metal ions to form polyolefin-based ionic polymers.

[0023] It has been discovered that polyolefin-based ionic polymers can have improved mechanical properties, such as toughness and elasticity, compared to their precursor copolymers that do not contain ionic groups. It has further been discovered that polyolefin-based ionic polymers can flow and can be reprocessed while also retaining one or more properties of crosslinked rubbers, such as toughness, elasticity, and resistance to heat, chemicals, and other environmental exposures. In some embodiments, unlike their precursor polymers, polyolefin-based ionic polymers can behave like physically crosslinked materials, such as crosslinked rubbers, at room temperature and can be reprocessed into new products at relatively higher temperatures. In some embodiments, polyolefin-based ionic polymers can behave as well as or better than soft ethylene propylene rubbers.

[0024] The term "and / or" means both the inclusive "and" and the exclusive "or", and is used herein in the same sense as "and / or" is used in the art. For example, a composition containing "A and / or B" can contain A alone, B alone, or both A and B; a composition containing "A or B" can contain A alone, B alone, or both A and B.

[0025] Percentages of particular monomers in polymers are expressed herein as weight percentages (wt%) based on the total weight of polymer present. Other percentages are expressed as weight percentages (wt%) based on the total weight of the particular composition present, unless otherwise specified. Room temperature is 25 °C ± 2 °C and atmospheric pressure is 101.325 kPa, unless otherwise specified.

[0026] For purposes herein, a "polymer" refers to a compound having two or more "monomer" units (see below for polyester monomer units), i.e., a degree of polymerization of 2 or greater, wherein the monomer units can be of the same or different species. A "homopolymer" is a polymer containing monomer units of the same species. A "copolymer" is a polymer having two or more different kinds of monomer units. A "terpolymer" is a polymer having three different kinds of monomer units. "Different" in relation to monomer units indicates that the monomer units differ from one another by at least one atom or are isomerically different. Unless otherwise indicated, polymers referred to herein include copolymers, terpolymers, or any polymer comprising repeating units of the same or different species.

[0027] The term "residue" or "unit" as used herein refers to the organic structure of a monomer in its polymerized form as introduced into a polymer, e.g., via polymerization of the respective monomer. Throughout the specification and claims, monomer(s) involved in a polymer are understood to refer to the respective polymerized form or residue of the respective monomer(s).

[0028] For purposes herein, the glass transition temperature is determined by the second heating ramp by heating the sample from 0°C to 300°C at 10°C / min by DSC analysis. The glass transition temperature is measured as the midpoint of the respective endothermic or exothermic curve in the second heating ramp.

[0029] For purposes herein, proton NMR spectra are collected using a suitable instrument, such as a 500 MHz Varian pulsed Fourier transform NMR spectrometer equipped with a variable temperature proton detection probe operating at 120°C. A typical measurement of NMR spectra includes dissolving a polymer sample in 1,1,2,2-tetrachloroethane-d2 ("TCE-d2") and transferring into a 5 mm glass NMR tube. Typical acquisition parameters are a scan width of 10 KHz, a pulse width of 30 degrees, an acquisition time of 2 seconds, an acquisition delay of 5 seconds, and 120 scans. Chemical shifts are determined relative to the TCE-d2 signal set at 5.98 ppm.

[0030] Dynamic mechanical thermal analysis ("DMTA") as used herein refers to analysis conducted according to procedures known in the art. Suitable instruments include those supplied by Rheometrics, Inc (TA Instruments, USA) unless otherwise specified. For purposes herein, samples are prepared as small rectangular samples, approximately 19.0 mm long x 5 mm wide x 0.5 mm thick. Polymer samples are molded on a Carver Lab Press or Wabash Press at about 190 °C. The polymer sample is then loaded between tool clamps at both ends into the open oven of the instrument. Once the sample is stabilized at the initial test temperature, the dimensions of the sample are recorded. After the oven and sample reach the initial test temperature of -80 °C, the test is started.

[0031] For purposes of the present disclosure, the new numbering scheme for groups of the periodic table as described in Chemical and Engineering News, v. 63(5), p. 27 (1985) is used, e.g., "Group 4 metal" is an element of Group 4 of the Periodic Table, e.g., Hf, Ti, or Zr.

[0032] "Olefins", or alternatively "olefins", are linear, branched, or cyclic compounds of carbon and hydrogen having at least one carbon-carbon double bond. For purposes of this specification and the claims appended hereto, when a polymer or copolymer is referred to as containing an olefin, the olefin present in such polymer or copolymer is in the polymerized form of the olefin. For example, when a copolymer is said to have a "ethylene" content of 35-55 wt%, it is to be understood that the monomer units in the copolymer are derived from ethylene in the polymerization reaction and the derived units are present at 35-55 wt% based on the weight of the copolymer. A "polymer" has two or more monomer units, which are the same or different. A "homopolymer" is a polymer containing the same monomer unit. A "copolymer" is a polymer having two or more different monomer units from each other. A "terpolymer" is a polymer having three different monomer units from each other. The term "different" as used in reference to monomer units indicates that the monomer units differ from each other by at least one atom or are isomerically different. Thus, the definition of copolymer used herein includes terpolymers and the like. An "ethylene polymer" or "ethylene copolymer" is a polymer or copolymer comprising at least 50 mol% of units derived from ethylene, a "propylene polymer" or "propylene copolymer" is a polymer or copolymer comprising at least 50 mol% of units derived from propylene, and so on.

[0033] For purposes of the present disclosure, ethylene is to be considered an alpha-olefin.

[0034] The terms "hydrocarbyl radical", "hydrocarbyl", and "hydrocarbyl group" are used interchangeably herein. Likewise, the terms "radical", "group", and "substituent" are also used interchangeably herein. For the purposes of the present disclosure, "hydrocarbyl" is defined as a group containing only hydrogen and up to 50 carbon atom(s) and can be linear, branched, or cyclic, and when cyclic, can be aromatic or non-aromatic.

[0035] Substituted hydrocarbyl is a group in which at least one hydrogen atom has been replaced with at least one functional group, such as NR x 2, OR x , SeR x , TeR x , PR x 2, AsR x 2, SbR x 2, SR x , BR x , or in which at least one non-hydrocarbon atom or group has been inserted in the hydrocarbyl group, such as -0-, -S-, -Se-, -Te-, -N(R x )-, =N-, -P(R x )-, =P-, -As(R x )-, =As-, -Sb(R x )-, =Sb-, -B(R x )-, =B-, and the like, where R x is independently a hydrocarbyl or halocarbyl, and two or more R x may join together to form a substituted or unsubstituted saturated, partially unsaturated, or aromatic, cyclic ring or ring system. Examples of substituted hydrocarbyl include -CH2CH2-0-CH3and -CH2-NMe2, where the groups are bonded through a carbon atom, but does not include groups where the groups are bonded through a heteroatom, such as -OCH2CH3or -NMe2.

[0036] Silylcarbyl is a group in which one or more hydrocarbyl hydrogen atoms has been replaced with at least one SiR*3-containing group or in which at least one -Si(R*)2- has been inserted in the hydrocarbyl group, where R* is independently a hydrocarbyl or halocarbyl, and two or more R* can join together to form a substituted or unsubstituted saturated, partially unsaturated, or aromatic, cyclic ring or ring system.

[0037] A substituted silylcarbyl group is a group in which at least one hydrogen atom has been replaced by at least one functional group, such as NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, BR*2, GeR*3, SnR*3, PbR*3, and the like, or in which at least one non-hydrocarbon atom or group has been inserted into the silylcarbyl group, such as -0-, -S-, -Se-, -Te-, -N(R*)-, =N-, -P(R*)-, =P-, -As(R*)-, =As-, -Sb(R*)-, =Sb-, -B(R*)-, =B-, -Ge(R*)2-, -Sn(R*)2-, -Pb(R*)2-, and the like, where R* is independently a hydrocarbyl or halocarbyl group, and two or more R* can join together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic ring structure.

[0038] A germylcarbyl group is a group in which one or more hydrocarbyl hydrogen atoms have been replaced by at least one GeR*3-containing group or in which at least one -Ge(R*)2- has been inserted into the hydrocarbyl group, where R* is independently a hydrocarbyl or halocarbyl group, and two or more R* can join together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic ring structure. A substituted germylcarbyl group is bonded only through carbon or germanium atoms.

[0039] A substituted germylcarbyl group is a group in which at least one hydrogen atom has been replaced by at least one functional group, such as NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, BR*2, SiR*3, SnR*3, PbR*3, and the like, or in which at least one non-hydrocarbon atom or group has been inserted into the germylcarbyl group, such as -0-, -S-, -Se-, -Te-, -N(R*)-, =N-, -P(R*)-, =P-, -As(R*)-, =As-, -Sb(R*)-, =Sb-, -B(R*)-, =B-, -Si(R*)2-, -Sn(R*)2-, -Pb(R*)2-, and the like, where R* is independently a hydrocarbyl or halocarbyl group, and two or more R* can join together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic ring structure.

[0040] A halocarbyl group is a group in which one or more hydrocarbyl hydrogen atoms have been replaced by at least one halogen (e.g., F, Cl, Br, I) or halogen-containing group (e.g., CF3).

[0041] A substituted halocarbyl group is one in which at least one halocarbyl hydrogen or halogen atom has been replaced by at least one functional group such as NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, BR*2, and the like, or in which at least one non-carbon atom or group has been inserted in the halocarbyl group, such as -0-, -S-, -Se-, -Te-, -N(R*)-, =N-, -P(R*)-, =P-, -As(R*)-, =As-, -Sb(R*)-, =Sb-, -B(R*)-, =B-, and the like, where R* is independently a hydrocarbyl or halocarbyl group, with the proviso that at least one halogen atom is retained on the original halocarbyl group. Additionally, two or more R* can join together to form a substituted or unsubstituted saturated, partially unsaturated, or aromatic ring structure. A substituted halocarbyl group is bonded only via carbon atoms.

[0042] The terms "aryl" or "aryl group" mean a monocyclic or polycyclic aromatic ring and substituted variations thereof, including but not limited to, phenyl, naphthyl, 2-methyl-phenyl, methylbenzyl, 4-bromo-methylbenzyl. Likewise "heteroaryl" means an aryl group in which a ring carbon atom (or two or three ring carbon atoms) has been replaced with a heteroatom, such as N, O, or S. The term "substituted aryl" means: 1) an aryl group in which a hydrogen has been replaced by a substituted or unsubstituted hydrocarbyl group, a substituted or unsubstituted halocarbyl group, a substituted or unsubstituted silylcarbyl group, or a substituted or unsubstituted germylcarbyl group. The term "substituted heteroaryl" means: 1) a heteroaryl group in which a hydrogen has been replaced by a substituted or unsubstituted hydrocarbyl group, a substituted or unsubstituted halocarbyl group, a substituted or unsubstituted silylcarbyl group, or a substituted or unsubstituted germylcarbyl group.

[0043] For numbering purposes the following numbering schemes are used for indenyl, trihydro-s-indacenyl, trihydro-as-indacenyl, tetrahydro-s-indacenyl, and tetrahydro-as-indacenyl ligands.

[0044]

[0045] As used herein, Mn is number average molecular weight, Mw is weight average molecular weight, Mz is z average molecular weight, wt% is weight percent, and mol% is mole percent. Molecular weight distribution (MWD), also referred to as polydispersity, is defined to be Mw divided by Mn. Unless otherwise indicated, all molecular weight units (e.g., Mw, Mn, Mz) are g / mol. The following abbreviations can be used herein: ENB is 5-ethylidene-2-norbornene, Me is methyl, Et is ethyl, Pr is propyl, cPr is cyclopropyl, nPr is normal propyl, iPr is iso-propyl, Bu is butyl, nBu is normal butyl, iBu is iso-butyl, sBu is sec-butyl, tBu is tert-butyl, Oct is octyl, Ph is phenyl, Bn is benzyl, Cp is cyclopentadienyl, Ind is indenyl, and MAO is methylaluminoxane.

[0046] For purposes herein, a "catalyst system" is a combination of at least one catalyst compound, at least one activator, optionally an activator-support, and optionally a support material. The catalyst systems described herein can or can not be supported (i.e., "heterogeneous"). For purposes of the present disclosure and the claims hereto, when a catalyst system is described as containing components in their neutral stable form, it is understood by those skilled in the art that the ionic form of the components is the form that is reacted with monomers to produce polymers.

[0047] In the description herein, metallocene catalysts can be described as catalyst precursors, procatalyst compounds, metallocene catalyst compounds, or transition metal compounds, and these terms are used interchangeably.

[0048] Metallocene catalysts are defined as organometallic transition metal compounds having at least one p-bonded cyclopentadienyl moiety (or substituted cyclopentadienyl moiety) bonded to the transition metal.

[0049] For purposes of the present disclosure related to metallocene catalyst compounds, the term "substituted" means that one or more hydrogen atoms have been replaced with a hydrocarbyl group, a heteroatom (e.g., halo), or a heteroatom-containing group (e.g., silylcarbyl, germylcarbyl, halocarbyl, etc.). For example, a methylcyclopentadiene (Cp) is a Cp group substituted with a methyl group.

[0050] For purposes of the present disclosure, "alkoxide" includes groups in which the alkyl group is a C1-C 10 Those of hydrocarbyl groups. Alkyl groups can be straight-chain, branched or cyclic alkyl groups. Alkyl groups can be saturated or unsaturated. In some embodiments, alkyl groups can comprise at least one aromatic group.

[0051] Copolymers

[0052] The copolymers of the present disclosure can have an alpha-olefin monomer, an optional comonomer, an optional diene, and a metal-alkenyl group, such as vinyl aluminum. For example, the copolymer can have greater than or equal to about 50 wt% and less than or equal to about 99.9 wt% of at least one C2-C20 alpha-olefin monomer, based on the total weight of the copolymer. 60 The copolymer can have greater than or equal to about 0.1 wt% and less than or equal to about 20 wt% of diene units, based on the total weight of the copolymer. The copolymer can have greater than or equal to about 0.1 wt% and less than or equal to about 10 wt% of vinyl aluminum units, based on the total weight of the copolymer.

[0053] In at least one embodiment, the copolymer can have an alpha-olefin monomer content of about 50 wt% to about 99.9 wt%, for example, about 60 wt% to about 99.9 wt%, for example, about 70 wt% to about 99.9 wt%, for example, about 80 wt% to about 99.5 wt%, for example, about 85 wt% to about 99 wt%, for example, about 90 wt% to about 99 wt%, for example, about 93 wt% to about 99 wt%, for example, about 95 wt% to about 99 wt%, based on the weight of the copolymer.

[0054] In at least one embodiment, the copolymer can have an optional comonomer content of about 0.1 wt% to about 49 wt%, for example, about 0.5 wt% to about 45 wt%, for example, about 1 wt% to about 40 wt%, for example, about 5 wt% to about 40 wt%, for example, about 10 wt% to about 35 wt%, for example, about 15 wt% to about 30 wt%, for example, about 20 wt% to about 30 wt%, for example, about 25 wt% to about 30 wt%, based on the weight of the copolymer.

[0055] The copolymer can further include an optional diene content of 0.01 wt% to about 20 wt% (for example, about 0.1 wt% to about 10 wt%, for example, about 0.5 wt% to about 5 wt%, for example, about 1 wt% to about 3 wt%, for example, about 1.5 wt% to about 3 wt%, based on the weight of the copolymer).

[0056] The copolymer can further include a metal-alkenyl content of about 0.01 wt% to about 20 wt% (for example, about 0.1 wt% to about 10 wt%, for example, about 0.1 wt% to about 5 wt%, for example, about 0.3 wt% to about 3 wt%, for example, about 0.5 wt% to about 1.5 wt%, based on the weight of the copolymer). The copolymer can also have a glass transition temperature of -100 °C to 5 °C and a Mw of 50 kg / mol to 5,000 kg / mol.

[0057] In at least one embodiment, the copolymer can comprise:

[0058] 1) propylene present at 50 wt% to about 99.89 wt% (e.g., about 70 wt% to about 99.5 wt%, e.g., about 80 wt% to about 99 wt%, e.g., about 90 wt% to about 99 wt%, based on the weight of the copolymer) with ethylene;

[0059] 2) ethylene present at 0.1 wt% to about 50 wt% (e.g., about 1 wt% to about 30 wt%, e.g., about 3 wt% to about 20 wt%, based on the weight of the copolymer);

[0060] 3) an optional diene present at 0.01 wt% to about 20 wt% (e.g., about 0.1 wt% to about 10 wt%, e.g., about 0.5 wt% to about 5 wt%, e.g., about 1 wt% to about 3 wt%, e.g., about 1.5 wt% to about 3 wt%, based on the weight of the copolymer); and

[0061] 4) a metal-alkenyl present at about 0.01 wt% to about 20 wt% (e.g., about 0.1 wt% to about 10 wt%, e.g., about 0.1 wt% to about 5 wt%, e.g., about 0.3 wt% to about 3 wt%, e.g., about 0.5 wt% to about 2.0, e.g., about 0.5 wt% to about 1.5 wt%, based on the weight of the copolymer); and

[0062] 5) a glass transition temperature of -60 to 5°C and a Mwof 50 to 5,000 kg / mol.

[0063] The monomers and optional comonomers independently include substituted or unsubstituted C2 to C 40 α-olefins, e.g., C2 to C 20 α-olefins, e.g., C2 to C 12 α-olefins, e.g., ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and isomers thereof. In at least one embodiment, the monomers include ethylene and an optional comonomer including one or more C3 to C 40 olefins, e.g., C4 to C 20 olefins, e.g., C6 to C 12 olefins. The C3 to C 40 The olefin monomers can be linear, branched, or cyclic. The C3 to C 40 The cyclic olefins can be strained or unstrained, monocyclic or polycyclic, and can optionally include heteroatoms and / or one or more functional groups. In another embodiment, the monomers include propylene and an optional comonomer including one or more ethylene or C4 to C 40 olefins, e.g., C4 to C 20olefins, such as C6to C 12 olefins. The C4to C 40 Olefins. The C4to C 40 Cyclic olefins can be strained or unstrained, monocyclic or polycyclic, and can optionally include heteroatoms and / or one or more functional groups.

[0064] Exemplary C2to C 40 Olefins and optional comonomers can include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclododecene, 7-oxanorbornene, substituted derivatives thereof, and isomers thereof, such as hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, norbornene, and their respective homologs and derivatives, such as norbornene.

[0065] In at least one embodiment, the alpha-olefin monomer or comonomer can be a linear alpha-olefin. Linear alpha-olefins (LAOs) can be substituted or unsubstituted C6-C 60 LAOs, such as C6-C 50 LAOs, such as C8-C 40 LAOs, such as C 10 -C 30 LAOs, such as C 10 -C 20 LAOs, such as C 15 -C 20 LAOs, or C8-C 16 LAOs, such as C8-C 12 LAOs. LAOs can have some branching. For example, LAOs can have one or more pendant methyl or ethyl groups along the LAO backbone. In some embodiments, LAOs are free of branching, e.g., are completely linear. In at least one embodiment, the copolymer has linear alpha-olefin units selected from the group consisting of 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, and combinations thereof.

[0066] In at least one embodiment, the copolymer can have an alpha-olefin content comprising ethylene and a comonomer content comprising propylene. The ethylene content can be from about 50 wt% to about 99.9 wt%, such as from about 50 wt% to about 99 wt%, such as from about 50 wt% to about 90 wt%, such as from about 50 wt% to about 80 wt%, such as from about 50 wt% to about 70 wt%, such as from about 50 wt% to about 60 wt%, such as from about 50 wt% to about 55 wt%, based on the weight of the copolymer. The propylene content can be from about 0.1 wt% to about 50 wt%, such as from about 1 wt% to about 50 wt%, such as from about 10 wt% to about 50 wt%, such as from about 20 wt% to about 50 wt%, such as from about 30 wt% to about 50 wt%, such as from about 40 wt% to about 50 wt%, such as from about 45 wt% to about 50 wt%, based on the weight of the copolymer.

[0067] In at least one embodiment, the copolymer can have an alpha-olefin content comprising ethylene and a comonomer content comprising propylene. The ethylene content can be from about 50 wt% to about 99.9 wt%, such as from about 50 wt% to about 99 wt%, such as from about 50 wt% to about 90 wt%, such as from about 50 wt% to about 80 wt%, such as from about 50 wt% to about 70 wt%, such as from about 50 wt% to about 60 wt%, such as from about 50 wt% to about 55 wt%, based on the weight of the copolymer. The propylene content can be from about 0.1 wt% to about 50 wt%, such as from about 1 wt% to about 50 wt%, such as from about 10 wt% to about 50 wt%, such as from about 20 wt% to about 50 wt%, such as from about 30 wt% to about 50 wt%, such as from about 40 wt% to about 50 wt%, such as from about 45 wt% to about 50 wt%, based on the weight of the copolymer.

[0068] In at least one embodiment, the copolymer can have a diene content of from about 0.1 wt% to about 40 wt%, such as from about 0.1 wt% to about 30 wt%, such as from about 0.1 wt% to about 20 wt%, such as from about 0.1 wt% to about 10 wt%, such as from about 0.5 wt% to about 10 wt%, such as from about 1 wt% to about 10 wt%, such as from about 1.5 wt% to about 8 wt%, such as from about 2 wt% to about 6 wt%, such as from about 2 wt% to about 5 wt%, or from about 8 wt% to about 12 wt%.

[0069] In at least one embodiment, the diene can be a substituted or unsubstituted diene selected from C4-C 60 The diene, such as C5-C 50 The diene, such as C5-C 40 The diene, such as C5-C 30 The diene, such as C5-C 20 The diene, such as C6-C 15dienes, such as C6-C 10 dienes, such as C7-C9 dienes, for example, substituted or unsubstituted C7 dienes, C8 dienes, or C9 dienes. In at least one embodiment, the copolymer has diene units of C7 dienes. In at least one embodiment, the diene is a substituted or unsubstituted a,co-diene (for example, the diene units of the copolymer are formed from di-vinyl monomers). The diene can be a linear di-vinyl monomer. In at least one embodiment, the diene is selected from butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, eicosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, and combinations (one or more) thereof. In some embodiments, the diene is selected from 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, and combinations (one or more) thereof. In at least one embodiment, the diene is selected from cyclopentadiene, vinyl norbornene, norbornadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, divinylbenzene, dicyclopentadiene, and combinations (one or more) thereof. In at least one embodiment, the copolymer has diene units of 5-ethylidene-2-norbornene.

[0070] In at least one embodiment, the copolymer can have a metal-alkenyl content of about 0.01 wt% to about 20 wt%, for example, about 0.1 wt% to about 10 wt%, for example, about 0.1 wt% to about 5 wt%, for example, about 0.3 wt% to about 3 wt%, for example, about 0.5 wt% to about 1.5 wt%, based on the weight of the copolymer.

[0071] The metal-alkenyl group is generally represented by the following formula:

[0072] Q(R′) z-v (R) v

[0073] where Q is a Group 1, 2, 12, or 13 metal, for example, Al, B, Ga, Mg, Li, or Zn; R is a hydrocarbyl group containing 4 to 20 carbon atoms having an allyl chain end, R' is a hydrocarbyl group containing 1 to 30 carbon atoms, z is 1, 2, or 3, v is 1, 2, or 3, where z-v is 0, 1, or 2.

[0074] Suitable metal alkyls can be vinyl aluminum (alkyl aluminum). In at least one embodiment, the metal alkyl can include a metal having a carbon chain with a vinyl end group and two additional bulky groups (such as isobutyl). The bulky groups can sterically hinder their respective Al-C bonds, making it difficult to insert CO2 at those positions, thereby facilitating selective insertion of CO2 on the side of the alkyl group with the vinyl chain end. In at least one embodiment, the vinyl aluminum unit can be a vinyl aluminum transfer agent (AVTA), which can be any aluminum reagent containing at least one transferable group having a terminal vinyl group (also referred to as an allyl chain end). The allyl chain end is represented by the formula H2C=CH— CH2—. "Allyl vinyl," "allyl chain end," "vinyl chain end," "vinyl-terminated," "allyl vinyl," "terminal vinyl," and "vinyl-terminated" are used interchangeably herein and refer to an allyl chain end. An allyl chain end is not a vinylidene chain end or a vinylene chain end.

[0075] Useful groups that can be bonded to a metal (e.g., aluminum) and contain an allyl chain end are represented by the formula CH2=CH— CH2— R—, where R represents a hydrocarbeneyl group or a substituted hydrocarbeneyl group, such as a Ci to C 20 alkylene, preferably methylene (CH2), ethylene [(CH2)2], propylenediene [(CH2)3], butylenediene [(CH2)4], pentylenediene [(CH2)5], hexylenediene [(CH2)6], heptylenediene [(CH2)7], octylenediene [(CH2)8], nonylenediene [(CH2)9], decylenediene [(CH2) 10 ]undecylenediene [(CH2) 11 ]dodecylenediene [(CH2) 12 ], or isomers thereof. Useful transferable groups are preferably unsubstituted linear hydrocarbeneyl groups.

[0076] In some embodiments, the vinyl aluminum is represented by the following formula (II):

[0077] Al(R′) 3-v (R) v

[0078] where R is a hydrocarbenyl containing 4 to 20 carbon atoms with an allyl chain end, R' is a hydrocarbyl containing 1 to 30 carbon atoms, v is 1 to 3, or v is 1.1 to 2.9, or 1.5 to 2.9, or 1.5 to 2.5, or 1.8 to 2.2. The formula Al(R') 3-v (R) vCompounds represented by formula (III) are typically neutral species, but anionic formulations, such as those represented by formula (III) are contemplated: [Al(R') 4-w (R) w ] - where w is 0.1 to 4, or 1.1 to 4, R is a hydrocarbyl group containing 4 to 50 carbon atoms having an allyl chain end, and R' is a hydrocarbyl group containing 1 to 50 carbon atoms.

[0079] In at least one embodiment of the formula of the vinyl aluminum transfer agent described herein, each R' is independently selected from the group consisting of C1to C 50 hydrocarbyl groups (e.g., C1to C 20 alkyl, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or isomers thereof), and R is represented by the formula:

[0080] —(CH2) n CH=CH2

[0081] where n is an integer from 2 to 18, preferably 5 to 18, preferably 5 to 12, preferably 5 to 6. In at least one embodiment, particularly useful AVs include isobutyl-di(oct-7-en-1-yl)-aluminum, isobutyl-di(dec-9-en-1-yl)-aluminum, isobutyl-di(non-8-en-1-yl)-aluminum, isobutyl-di(hept-6-en-1-yl)-aluminum, dimethyl(oct-7-en-1-yl)aluminum, diethyl(oct-7-en-1-yl)aluminum, dibutyl(oct-7-en-1-yl)aluminum, diisobutyl(oct-7-en-1-yl)aluminum, diisobutyl(non-8-en-1-yl)aluminum, diisobutyl(dec-9-en-1-yl)aluminum, diisobutyl(dodec-10-en-1-yl)aluminum, diisobutyl(hept-6-en-1-yl)aluminum, diethyl(hept-6-en-1-yl)aluminum, dimethyl(hept-6-en-1-yl)aluminum, and the like. Mixtures of one or more AVs can also be used. In some embodiments, isobutyl-di(oct-7-en-1-yl)-aluminum, isobutyl-di(dec-9-en-1-yl)-aluminum, and / or isobutyl-di(non-8-en-1-yl)-aluminum, isobutyl-di(hept-6-en-1-yl)-aluminum are used.

[0082] Useful vinyl aluminum compounds include aluminum reagents (AlR a3) Reaction products of organoaluminum compounds with alkyl dienes. Suitable alkyl dienes include those having two "alpha-olefins" at both ends of the carbon chain. The alkyl dienes can be straight or branched alkyl chains and substituted or unsubstituted. Exemplary alkyl dienes include, but are not limited to, for example, 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, 1,14-pentadecadiene, 1,15-hexadecadiene, 1,16-heptadecadiene, 1,17-octadecadiene, 1,18-nonadecadiene, 1,19- eicosadiene, 1,20-heneicosadiene, and the like. Exemplary aluminum reagents include triisobutylaluminum, diisobutylaluminum hydride, isobutylaluminum dihydride, and aluminum hydride (AlH3).

[0083] In any embodiment of the application described herein, R is butenyl, pentenyl, heptenyl, or octenyl. In some embodiments, R is octenyl.

[0084] In any embodiment of the application described herein, R' is methyl, ethyl, propyl, isobutyl, or butyl. In some embodiments, R' is isobutyl.

[0085] In any embodiment of the application described herein, Rais methyl, ethyl, propyl, isobutyl, or butyl. In some embodiments, Rais isobutyl.

[0086] In any embodiment of the application described herein, v is about 2, or v is 2.

[0087] In yet another aspect, the vinyl aluminum units have less than 50 wt% of dimers present, based on the weight of the AV, for example, less than 40 wt%, for example, less than 30 wt%, for example, less than 20 wt%, for example, less than 15 wt%, for example, less than 10 wt%, for example, less than 5 wt%, for example, less than 2 wt%, for example, less than 1 wt%, for example, 0 wt% of dimers. Alternatively, the dimers are present in an amount of 0.1 to 50 wt%, or 1 to 20 wt%, or 2 to 10 wt%. The dimers are dimerization products of the alkyl diene used to make the AV. The dimers can form under certain reaction conditions and are formed by insertion of a diene molecule into the Al-R bond of the AV followed by beta-hydride elimination (see US 2018-0194872 Figure 4 ). For example, if the alkyl diene used is 1,7-octadiene, the dimer is 7-methylene pentadeca-1,14-diene. Similarly, if the alkyl diene is 1,9-decadiene, the dimer is 9-methylene nonadeca-1,18-diene.

[0088] Useful AV compounds can be prepared by combining an alkyl aluminum having at least one secondary alkyl moiety (aluminum reagent) such as triisobutyl aluminum and / or at least one hydride such as a dialkyl aluminum hydride, a monoalkyl aluminum dihydride, or aluminum trihydride (aluminum hydride, AlH3) with an alkyl diene and heating to a temperature that causes release of the alkylidene byproduct. The reaction can be in the absence of solvent (neat) or in the presence of a nonpolar, noncoordinating solvent such as C5-C10 alkanes or aromatic solvents such as hexane, pentane, toluene, benzene, xylene, and the like or combinations thereof. The reaction is preferably heated from 60 °C to 110 °C. Lower reaction temperatures of 60 °C to 80 °C are preferred if longer reaction times are used, for example, heating and stirring for 6-24 hours. Higher reaction temperatures of 90 °C to 110 °C are preferred if shorter reaction times are used, for example, heating and stirring for 1 to 2 hours. At reaction temperatures of 65 °C to 75 °C, the reaction is preferably heated and stirred for 6-18 hours, preferably 8-12 hours. At reaction temperatures of 100 °C to 110 °C, the reaction is preferably heated and stirred for 1 to 2 hours. Combinations of high and low reaction temperatures can be used, for example, heating and stirring the reaction at 110 °C for 1 hour and then heating and stirring at 65 °C to 75 °C for 8-12 hours. Longer reaction times at lower reaction temperatures or shorter reaction times at higher reaction temperatures favor the formation of AVs with v = 2 and disfavor the formation of dimers. AVs with v = 3 typically occur at higher reaction temperatures and longer times and are accompanied by dimer formation. 10 The reaction can be in the absence of solvent (neat) or in the presence of a nonpolar, noncoordinating solvent such as C5-C10 alkanes or aromatic solvents such as hexane, pentane, toluene, benzene, xylene, and the like or combinations thereof. The reaction is preferably heated from 60 °C to 110 °C. Lower reaction temperatures of 60 °C to 80 °C are preferred if longer reaction times are used, for example, heating and stirring for 6-24 hours. Higher reaction temperatures of 90 °C to 110 °C are preferred if shorter reaction times are used, for example, heating and stirring for 1 to 2 hours. At reaction temperatures of 65 °C to 75 °C, the reaction is preferably heated and stirred for 6-18 hours, preferably 8-12 hours. At reaction temperatures of 100 °C to 110 °C, the reaction is preferably heated and stirred for 1 to 2 hours. Combinations of high and low reaction temperatures can be used, for example, heating and stirring the reaction at 110 °C for 1 hour and then heating and stirring at 65 °C to 75 °C for 8-12 hours. Longer reaction times at lower reaction temperatures or shorter reaction times at higher reaction temperatures favor the formation of AVs with v = 2 and disfavor the formation of dimers. AVs with v = 3 typically occur at higher reaction temperatures and longer times and are accompanied by dimer formation.

[0089] After the reaction is complete, the solvent, if present, can be removed and the product can be used directly without further purification.

[0090] In at least one embodiment, the copolymer can have a vinyl aluminum content of about 0.01 wt% to about 20 wt%, for example, about 0.1 wt% to about 10 wt%, for example, about 0.1 wt% to about 5 wt%, for example, about 0.3 wt% to about 3 wt%, for example, about 0.5 wt% to about 1.5 wt%, based on the weight of the copolymer.

[0091] In at least one embodiment, the metal alkyl can be an alkyl borane unit. In at least one embodiment, the alkyl borane unit can be any of the vinyl aluminum units listed herein with borane substituted for aluminum.

[0092] In at least one embodiment, the copolymer can have an alkyl borane content of about 0.01 wt% to about 20 wt%, for example, about 0.1 wt% to about 10 wt%, for example, about 0.1 wt% to about 5 wt%, for example, about 0.3 wt% to about 3 wt%, for example, about 0.5 wt% to about 1.5 wt%, based on the weight of the copolymer.

[0093] In at least one embodiment, the metal alkylidene can be an alkenyl magnesium unit. In at least one embodiment, the alkenyl magnesium unit can be any of the magnesium vinyl units listed herein having another Group 13 metal substituted for aluminum.

[0094] In at least one embodiment, the copolymer can have an alkenyl magnesium content of about 0.01 wt% to about 20 wt%, such as about 0.1 wt% to about 10 wt%, such as about 0.1 wt% to about 5 wt%, such as about 0.3 wt% to about 3 wt%, such as about 0.5 wt% to about 1.5 wt%, based on the weight of the copolymer.

[0095] In at least one embodiment, the metal alkylidene can include any suitable compound having a metal and a vinyl end group. In at least one embodiment, the metal alkylidene can include any Group 13 metal, such as B, Al, Ga, In. In at least one embodiment, the metal alkylidene can include any of the vinyl aluminum units listed herein having another Group 13 metal substituted for aluminum.

[0096] In at least one embodiment, the metal alkylidene can include any Group 1, 2, or 12 metal, such as Li, Mg, or Zn. In at least one embodiment, the metal alkylidene can include any of the vinyl aluminum units listed herein having another Group 1, 2, or 12 metal substituted for aluminum.

[0097] Once polymerization has been carried out, the copolymer can have pendant metal groups, such as pendant aluminum groups. In other embodiments, the copolymer can have pendant groups of B, Ga, In, Li, Mg, or Zn.

[0098] As described in more detail below, the copolymer can be treated with a suitable reagent such that the pendant aluminum groups (or other pendant groups having Group 1, 2, 12, or 13 atoms) are modified to form a copolymer having pendant carboxylate or sulfonate groups.

[0099] For methods of synthesis of vinyl aluminum compounds, see US 2018 / 0194872.

[0100] Copolymer Properties

[0101] In at least one embodiment, the copolymer can have a Mw value of about 5,000 g / mol or greater, for example, from about 5,000 g / mol to about 2,000,000 g / mol, for example, from about 10,000 g / mol to about 1,000,000 g / mol, for example, from about 10,000 g / mol to about 500,000 g / mol, for example, from about 10,000 g / mol to about 300,000 g / mol, for example, from about 20,000 g / mol to about 200,000 g / mol, for example, from about 20,000 g / mol to about 100,000 g / mol, for example, from about 30,000 g / mol to about 90,000 g / mol, for example, from about 40,000 g / mol to about 80,000 g / mol. For example, from about 50,000 g / mol to about 70,000 g / mol, for example, from about 55,000 g / mol to about 65,000 g / mol, for example, from about 60,000 g / mol to about 65,000 g / mol.

[0102] In at least one embodiment, the copolymer can have a Mn value of 1,000 g / mol or greater, for example, from about 1,000 g / mol to about 400,000 g / mol, for example, from about 1,000 g / mol to about 200,000 g / mol, for example, from about 1,000 g / mol to about 100,000 g / mol, for example, from about 1,000 g / mol to about 50,000 g / mol, for example, from about 5,000 g / mol to about 40,000 g / mol, for example, from about 10,000 g / mol to about 30,000 g / mol, for example, from about 15,000 g / mol to about 25,000 g / mol, for example, from about 18,000 g / mol to about 20,000 g / mol.

[0103] In at least one embodiment, copolymers having a lower Mw value can be effective in coating applications. In at least one embodiment, copolymers having a higher Mw value can be effective for materials that undergo many loading / unloading cycles, such as tires. In at least one embodiment, copolymers having a Mw value of about 400,000 g / mol or greater can be effective for use in certain rubbers.

[0104] In at least one embodiment, the copolymer can have a Mw / Mn (polydispersity index) value of from about 1 to about 10, for example, from about 2 to about 5, for example, from about 3 to about 4.

[0105] Due to strong ion clustering, ionomers are generally insoluble in any solvent. The moment of the molecular weight of the metal-ene containing copolymer is determined by acidifying the ionomers to make them soluble in trichlorobenzene TCB. The acidified copolymer is then subjected to gel permeation chromatography (GPC), see experimental section below, to measure the moment of the molecular weight. For the purposes of the present invention and the appended claims, the moment of the molecular weight of the acidified polymer shall be considered as the moment of the molecular weight of the polymer before acidification.

[0106] In at least one embodiment, the copolymer can have a glass transition temperature (Tg) of -30°C or less, for example, from about -30°C to about -100°C, for example, from about -40°C to about -60°C, for example, from about -45°C to about -55°C, for example, from about -48°C to about -52°C, for example, from about -49°C to about -50°C, or from about -51°C to about -52°C, as determined by differential scanning calorimetry (DSC) as described below.

[0107] The comonomer composition can be determined by NMR, corresponding to the ratio of IR5 detector intensities of CH2and CH3channels calibrated with a series of PE and PP homopolymer / copolymer standards whose nominal values are pre-determined by NMR or FTIR. In particular, this provides the methyl / 1,000 total carbons (CH3 / 1000TC) as a function of molecular weight. The short chain branch (SCB) content / 1000TC (SCB / 1000TC) as a function of molecular weight is then calculated by applying a chain end correction to the CH3 / 1000TC functionality, assuming each chain to be linear and terminated by a methyl group at each end. The comonomer weight % is then obtained from the following expression, where f is 0.3, 0.4, 0.6, 0.8, etc. for C3, C4, C6, C8, etc. comonomers, respectively:

[0108] w2 = f * SCB / 1000TC.

[0109] The bulk composition of the polymer from GPC-IR and GPC-4D analysis is obtained by considering the total signal of the CH3and CH2channels between the integration limits of the concentration chromatogram. First, the following ratio is obtained

[0110]

[0111] The same calibration of the CH3and CH2signal ratio is then applied (as mentioned previously in obtaining CH3 / 1000TC as a function of molecular weight) to obtain the base CH3 / 1000TC. The bulk methyl chain ends / 1000TC (bulk CH3ends / 1000TC) is obtained by weight-averaging the chain end correction over the molecular weight range. Then

[0112] w2b = f * bulk CH3 / 1000 TC

[0113] bulk SCB / 1000 TC = bulk CH3 / 1000 TC - bulk CH3 end / 1000 TC

[0114] Ionic polymer

[0115] The ionic polymer of the present disclosure can have a copolymer and a metal cation content. After the copolymer is oxidized by introducing an oxidizing agent into a reactor, an ionic polymer having an alpha-olefin content and an anionic alkenyl content can be formed. In other words, metal alkenyl moieties of the copolymer are converted into anionic alkenyl moieties to form the ionic polymer, where the copolymer can have any of the comonomer compositions described herein.

[0116] In at least one embodiment, the ionic polymer can have from about 50 wt% to about 99.9 wt% C2-C 60 alpha-olefin units, based on the weight of the copolymer; and from about 0.1 wt% to about 10 wt% anionic alkenyl units, based on the weight of the ionic polymer. In at least one embodiment, the anionic alkenyl units have the formula— R(A )—, where R is an alkyl group containing 2 to 10 carbon atoms, where A is an anionic group. The above formula indicates that the alkyl group represented by R is divalent along with the rest of the polymer backbone. In at least one embodiment, the anionic group is carboxylate, and the anionic alkenyl units have the formula— R(-R A X COOAl(OR B )2)—, where R is preferably a linear, branched, or cyclic alkyl group containing 2 to 40 carbon atoms, R A is a hydrocarbyl group (typically an alkyl group containing 2 to 18 carbon atoms), R B is a hydrocarbyl group (typically an alkyl group containing 2 to 18 carbon atoms), and X is 0 or 1, indicating the presence or absence of a hydrocarbyl group.

[0117]

[0118] In at least one embodiment, the copolymer can have pendant carboxylate anion groups. In at least one embodiment, the copolymer can have pendant carboxylic acid groups. In at least one embodiment, the copolymer can have pendant sulfonate anion groups. In at least one embodiment, the copolymer can have pendant sulfonic acid groups. In at least one embodiment, the copolymer can have pendant phosphonate anion groups. In at least one embodiment, the copolymer can have pendant phosphonic acid groups. In at least one embodiment, the copolymer can include each acid group and its corresponding anion, depending on the dissociation constant of each pendant acid group in solution.

[0119] In at least one embodiment, the anionic alkenyl units can include carboxylate anions. In at least one embodiment, the copolymer can have a carboxylate anion alkenyl unit content of about 0.01 wt% to about 20 wt%, such as about 0.1 wt% to about 10 wt%, such as about 0.1 wt% to about 5 wt%, such as about 0.3 wt% to about 3 wt%, such as about 0.5 wt% to about 1.5 wt%, based on the weight of the copolymer.

[0120] In at least one embodiment, the anionic alkenyl units can include sulfonate anions. In at least one embodiment, the ionic polymer can have a sulfonate anion alkenyl unit content of about 0.01 wt% to about 20 wt%, such as about 0.1 wt% to about 10 wt%, such as about 0.1 wt% to about 5 wt%, such as about 0.3 wt% to about 3 wt%, such as about 0.5 wt% to about 1.5 wt%, based on the weight of the ionic polymer.

[0121] In at least one embodiment, the anionic alkenyl units can include phosphonate anions. In at least one embodiment, the ionic polymer can have a phosphonate anion alkenyl unit content of about 0.01 wt% to about 20 wt%, such as about 0.1 wt% to about 10 wt%, such as about 0.1 wt% to about 5 wt%, such as about 0.3 wt% to about 3 wt%, such as about 0.5 wt% to about 1.5 wt%, based on the weight of the copolymer.

[0122] In at least one embodiment, the ionic polymer has a metal cation. The metal cation can include any suitable metal. In at least one embodiment, the metal cation can be selected from the group consisting of alkali metals, alkaline earth metals, Group 3-12 metals, Group 13-16 metals, and combinations (one or more) thereof. In at least one embodiment, the alkali metals can include Li, Na, K, Rb, Cs, Fr, or combinations (one or more) thereof, such as Li, Na, and K; the alkaline earth metals can include Be, Mg, Ca, Sr, Ba, Ra, or combinations (one or more) thereof, such as Mg and Ca; and the Group 12 metals can include Zn, Cd, Hg, Cn, or combinations (one or more) thereof, such as Zn. In at least one embodiment, the metal cation can include Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Mn, Tc, Re, Bh, Fe, Ru, Os, Hs, Co, Rh, Ir, Mt, Ni, Pd, Pt, Ds, Cu, Ag, Au, Rg, Al, Ga, In, Tl, Nh, Sn, Pb, Fl, Bi, Mc, Po, Lv, or combinations (one or more) thereof.

[0123] Methods of making ionic polymers

[0124] In at least one embodiment, the method of making the ionic polymer can include introducing a metal cation into a copolymer having a pendant anion or acid group.

[0125] In at least one embodiment, the metal cation can be introduced into the copolymer by adding a solution containing the metal cation. In at least one embodiment, the metal cation is bonded to a basic compound, such as an anion. In at least one embodiment, the base can include a t-butoxide, a hydroxide, or any other suitable anion, including halides, sulfates, nitrates, nitrites, sulfides, phosphates, borates, and aluminate. For example, the anion can be selected from the group consisting of sodium t-butoxide, potassium t-butoxide, sodium hydroxide, potassium hydroxide, or combinations (one or more) thereof. In at least one embodiment, the suitable anion can be a bulky anion, such as t-butoxide or borate.

[0126] In at least one embodiment, the base can be dissolved in an alcohol, such as methanol (e.g., in a mixed solvent, such as 90:10 toluene / alcohol), or in any other suitable solvent.

[0127] In at least one embodiment, an ion exchange occurs between the metal cation and the pendant anion group to form the ionic polymer having a metal cation content.

[0128] In at least one embodiment, the concentration of metal cations can be about 0.05 wt% to about 30 wt%, such as about 1 to about 25 wt% or about 5 to about 20 wt%, based on the total weight of the ionomer. The concentration of metal cations is also in the range of a lower limit of about 1, 5, or 10 wt% to an upper limit of about 15, 25, or 30 wt%, based on the total weight of the ionomer.

[0129] In at least one embodiment, the ion exchange is conducted at a reactor temperature of about 23 °C or greater, such as 23 °C to about 150 °C, such as about 40 °C to about 100 °C, such as about 50 °C to about 90 °C, such as about 60 °C to about 80 °C, such as about 65 °C to about 75 °C, such as about 70 °C.

[0130] Ionomer Properties

[0131] In at least one embodiment, the ionomers prepared herein can have a weight average molecular weight (Mw) of at least 50,000 g / mol, such as 50,000 to 1,000,000 g / mol, such as 75,000 to 600,000 g / mol.

[0132] In at least one embodiment, the ionomers prepared herein can have a number average molecular weight (Mn) of at least 21,000 g / mol, such as 50,000 to 2,500,000 g / mol, such as 75,000 to 2,000,000 g / mol, such as 250,000 to 1,500,000 g / mol.

[0133] In at least one embodiment, the ionomers prepared herein can have a molecular weight distribution (Mw / Mn) of about 1.01 to 10, such as 1.5 to 6, such as 2 to 4.

[0134] In at least one embodiment, the ionomers prepared herein have a Mw / Mn of about 2 to about 4, and a Mw of about 50,000 g / mol or greater, and a Mn of about 21,000 g / mol or greater.

[0135] In at least one embodiment, the ionomers can have a maximum elastic range (yield strain %) of about 100% strain or greater, such as about 300% or greater, such as about 400% or greater, or about 100% strain to about 1,000% strain, such as about 200% strain to about 800% strain, such as about 300% strain to about 600% strain, such as about 400% strain to about 500% strain, such as about 460% strain, when determined according to ASTM D638.

[0136] In at least one embodiment, the ionomer can have a strain at break of about 100% or greater, for example about 300% or greater, for example about 500% or greater, or from about 100% to about 1,000%, for example from about 200% to about 800%, for example from about 400% to about 700%, for example from about 500% to about 600%, for example about 570%, when determined according to ASTM D638.

[0137] In at least one embodiment, the ionomer can have a tensile set of about 100% or less, for example from about 0% to about 80%, for example from about 20% to about 60%, for example from about 40% to about 50%, for example about 45%, at 200% strain.

[0138] In at least one embodiment, the ionomer can have an elastic modulus (Young’s modulus, E) of less than or equal to about 5 MPa, less than or equal to about 4 MPa, less than or equal to about 3 MPa, less than or equal to about 2 MPa, or less than or equal to about 1 MPa at 40 °C.

[0139] In at least one embodiment, the ionomer can have a glass transition temperature (Tg) of -30 °C or less, for example from about -30 °C to about -100 °C, for example from about -40 °C to about -60 °C, for example from about -45 °C to about -55 °C, for example from about -48 °C to about -52 °C, for example from about -49 °C to about -50 °C, or from about -51 °C to about -52 °C, as determined by differential scanning calorimetry (DSC) as described below. g ), as determined by differential scanning calorimetry (DSC) as described below.

[0140] In at least one embodiment, the ionomer can have a crystallization temperature (Tc) of from about -50 °C to about 100 °C, for example from about -30 °C to about 80 °C, for example from about -10 °C to about 60 °C, for example from about 10 °C to about 40 °C, as determined by differential scanning calorimetry (DSC) as described below. c ), as determined by differential scanning calorimetry (DSC) as described below.

[0141] In at least one embodiment, the ionomer can have a melting temperature (Tm) of from about -45 °C to about 105 °C, for example from about -25 °C to about 85 °C, for example from about -5 °C to about 65 °C, for example from about 15 °C to about 45 °C, as determined by differential scanning calorimetry (DSC) as described below. m ), as determined by differential scanning calorimetry (DSC) as described below.

[0142] In at least one embodiment, the ionomer can have a heat of fusion (Hf) of from about 5 J / g to about 100 J / g, for example from about 15 J / g to about 80 J / g, for example from about 25 J / g to about 60 J / g, for example from about 35 J / g to about 40 J / g, as determined by differential scanning calorimetry (DSC) as described below. f ), as determined by differential scanning calorimetry (DSC) as described below.

[0143] In at least one embodiment, the ionic polymer can have a crystallinity (X c ) of about 0% to about 65%, for example, about 10% to about 55%, for example, about 20% to about 45%, for example, about 30% to about 35%.

[0144] In at least one embodiment, the ionic polymer can have a Young’s modulus (E) of about 0.1 to about 50 MPa, for example, about 0.2 to about 20 MPa, for example, about 0.5 to about 10 MPa, for example, about 1 to about 5 MPa.

[0145] In at least one embodiment, the ionic polymer can have an ultimate tensile strength of about 1 to about 25 MPa, for example, about 2 to about 20 MPa, for example, about 5 to about 15 MPa, for example, about 10 to about 12.5 MPa.

[0146] In at least one embodiment, the ionic polymer can have an elongation at break of about 20 to about 800%, for example, about 50 to about 600%, for example, about 100 to about 400%, for example, about 150 to about 200%.

[0147] The properties of the ionic polymer can be influenced by the ionic content. In this regard, the ionic content can be increased by at least one of: increasing the vinyl aluminum unit content in the copolymer precursor, increasing the extent of oxidation reaction to increase conversion of aluminum pendant groups to carboxylate anions, increasing the extent of ion exchange to facilitate conversion of the ionic polymer, or combinations thereof. In any case, the ionic content can be increased, thereby forming a stronger ionic network.

[0148] In at least one embodiment, the extent of oxidation reaction normalized to the initial number of moles of metal in the metal alkenyl compound can be about 0.5 to 1, for example, about 0.7 to 1, for example, about 0.9 to 1. The extent of oxidation reaction can be determined by measuring the consumption of distal hydrocarbyl groups bonded to the metal alkenyl via NMR.

[0149] In at least one embodiment, the extent of ion exchange normalized to the initial number of moles of anions can be about 0.5 to 1, for example, about 0.7 to 1, for example, about 0.9 to 1. The extent of ion exchange can be determined by measuring the concentration of metal cations in the ionic polymer compared to a standard solution of metal cations via FTIR spectra.

[0150] The properties of the ionic polymer can be influenced by temperature. For example, to rework an ionic polymer article, the temperature can be increased to decrease the overall ionic strength of the ionic polymer and increase the ability of the ionic polymer to flow. This ability to change the shape of the ionic polymer at elevated temperatures can improve molding applications.

[0151] In at least one embodiment, the ionic polymer can have local ionic clusters. Such ionic clusters can provide an ionic polymer that exhibits similar physical behavior as crosslinked rubber.

[0152] Additives

[0153] The ionic polymers of the present disclosure can be mixed with one or more additives to form an ionic polymer composition. The additives can include reinforcing and non-reinforcing fillers, antioxidants, stabilizers, processing oils (or other solvent(s)), compatibilizers, lubricants (e.g., oleamide), antiblocking agents, antistatic agents, waxes, coupling agents for fillers and / or pigments, pigments, flame retardants, antioxidants, or other processing aids or combinations thereof.

[0154] The ionic polymer compositions of the present disclosure can include additives such that the additives (e.g., fillers of the present disclosure (present in the composition)) have an average agglomerate size of less than 50 microns, for example, less than 40 microns, for example, less than 30 microns, for example, less than 20 microns, for example, less than 10 microns, for example, less than 5 microns, for example, less than 1 micron, for example, less than 0.5 microns, for example, less than 0.1 microns, based on a 1 cm x 1 cm cross-section of the ionic polymer observed using a scanning electron microscope.

[0155] In some embodiments, the ionic polymer composition can include fillers and colorants. Exemplary materials include inorganic fillers such as calcium carbonate, clay, silica, talc, titanium dioxide, or carbon black. Any suitable type of carbon black can be used, such as channel black, furnace black, thermal black, acetylene black, lamp black, and the like.

[0156] In some embodiments, the ionic polymer composition can include a flame retardant, such as calcium carbonate, inorganic clay containing water of hydration, such as aluminum trihydroxide ("ATH") or magnesium hydroxide.

[0157] In some embodiments, the ionic polymer composition can include a UV stabilizer, such as titanium dioxide or XT-850. The UV stabilizer can be introduced into the composition as part of a masterbatch. For example, the UV stabilizer can be pre-blended into a masterbatch with a thermoplastic resin (e.g., polypropylene) or polyethylene (e.g., linear low density polyethylene).

[0158] Still other additives can include antioxidants and / or heat stabilizers. In one exemplary embodiment, the processing and / or in-service heat stabilizers can include B-225 and / or 1010.

[0159] In some embodiments, the ionic polymer composition can include a polymer processing additive. The processing additive can be a polymer resin having a very high melt flow index. These polymer resins can include linear and branched polymers having a melt flow rate of about 500 dg / min or more, such as about 750 dg / min or more, such as about 1,000 dg / min or more, such as about 1,200 dg / min or more, such as about 1,500 dg / min or more. Mixtures of various branched or various linear polymer processing additives can be employed, as well as mixtures of both linear and branched polymer processing additives. Unless otherwise specified, references to polymer processing additives can include both linear and branched additives. Linear polymer processing additives include polypropylene homopolymers, branched polymer processing additives include diene-modified polypropylene polymers.

[0160] In some embodiments, the ionic polymer compositions of the present disclosure can optionally include reinforcing and non-reinforcing fillers, antioxidants, stabilizers, rubber processing oils, lubricants, antiblocking agents, antistatic agents, waxes, blowing agents, pigments, flame retardants, nucleating agents, and other processing aids known in the rubber compounding art. These additives can comprise up to about 50 wt% of the total composition.

[0161] Fillers and extenders that can be used include conventional inorganics such as calcium carbonate, clay, silica, talc, titanium dioxide, carbon black, nucleating agents, mica, wood flour, and the like and blends thereof, as well as inorganic and organic nanoscale fillers.

[0162] Molded articles

[0163] The ionic polymers (or compositions thereof) described herein can be used to make molded articles in any molding process, including but not limited to injection molding, gas-assisted injection molding, extrusion blow molding, injection blow molding, injection stretch blow molding, compression molding, roto-molding, foam molding, thermoforming, sheet extrusion, and profile extrusion.

[0164] In addition, the ionic polymers (or compositions thereof) described herein can be shaped into a desired end-use article by any suitable means. Suitable examples include thermoforming, vacuum forming, blow molding, rotational molding, hollow molding, transfer molding, wet lay-up or contact molding, casting, cold forming, match-die molding, injection molding, spray techniques, profile co-extrusion, or combinations thereof.

[0165] Thermoforming is a process of shaping at least one flexible plastic sheet into a desired shape. Typically, an extrudate film of the composition (and any other layers or materials) is placed on a shuttle to hold the film during heating. The shuttle indexes into an oven, which preheats the film prior to forming. Once the film is heated, the shuttle indexes back to the forming tool. The film is then vacuumed onto the forming tool to hold it in place and the forming tool is closed. The tool remains closed to cool the film, then the tool is opened. The formed laminate is then removed from the tool. Once the sheet of material reaches the thermoforming temperature, typically 140°C to 185°C or higher, thermoforming is accomplished by vacuum, positive air pressure, plug-assisted vacuum forming, or combinations and variations thereof. Particularly for large parts, a pre-stretch bubble step is used to improve material distribution.

[0166] Blow molding is another suitable forming means for the composition, which includes injection blow molding, multi-layer blow molding, extrusion blow molding, and stretch blow molding, and is particularly suitable for substantially closed or hollow objects, such as gas tanks and other fluid containers. Blow molding is described in more detail, for example, in Concise Encyclopedia of Polymer Science and Engineering, pp. 90-92 (Jacqueline I. Kroschwitz, ed., John Wiley & Sons 1990).

[0167] Similarly, molded articles can be made by injecting molten polymer into a mold that shapes and solidifies the molten polymer into a molded article of the desired geometry and thickness. Sheets can be prepared by extruding a substantially flat profile from a die onto a chill roll or by calendering.

[0168] Nonwoven and Fibrous Articles

[0169] The ionic polymers (or compositions thereof) described herein can be used to make nonwoven fabrics and fibers in any nonwoven fabric and fiber making process, including but not limited to, meltblowing, spunbonding, film hole, and staple fiber carding. Examples include continuous filament processes, spunbond processes, and the like. Spunbond processes include extruding fibers through a spinneret. The fibers are then drawn using a high velocity air stream and laid down on a circular belt. The web is then generally heated using a calender roll and the fibers are bonded to one another, although other techniques can be used such as sonic bonding and adhesive bonding.

[0170] The ionomer (or composition thereof) according to the embodiments disclosed herein can be used in a wide variety of applications, such as automotive overmold parts (e.g., door handles and housings, such as instrument panels, dashboards, and door inner and outer housings), airbag covers, toothbrush handles, shoe soles, handles, housings, toy, appliance moldings and pallets, gaskets, furniture moldings, and the like.

[0171] Other commercial articles that can be made include, but are not limited to, the following examples: awning and awning-coated fabrics, tent / tarpaulin-coated fabric covers, window shade extruded soft sheeting, coverall-coated fabrics, bumper fascia, instrument panels and trim panels, coated fabrics for use in automotive interiors, geotextiles, appliance door gaskets, grommets, gaskets / pads / cushions, hoses and tubing, syringe plunger tips, lightweight conveyor belt PVC replacements, modifiers for rubber concentrates to reduce viscosity, single ply roofing compositions, recreational and sporting goods, pen holders, razors, toothbrushes, handles, and the like. Other articles include marine bungee cords, pillow tanks, pipes, dunnage bags, architectural trim and moldings, collapsible storage containers, synthetic wine bottle stoppers, IV and fluid administration bags, examination gloves, and the like.

[0172] Exemplary articles made using the ionomer (or composition thereof) include cookware, storage appliances, toys, medical devices, sterilizable medical devices, sterilization containers, sheeting, crates, containers, packaging, wire and cable jacketing, pipes, geomembranes, sports equipment, chair cushions, tubing, profiles, instrument sample holders and sample windows, outdoor furniture such as garden furniture, playground equipment, automotive, boat and watercraft components, and other such articles. In particular, the ionomer (or composition thereof) is suitable for use in automotive parts such as bumpers, grilles, trim parts, instrument panels and dashboards, outer door and hood parts, spoilers, windshields, hubcaps, mirror housings, body panels, protective side moldings, and other interior and exterior components associated with automobiles, trucks, boats, and other vehicles. The ionomer can be used to make "soft touch" handles in products such as personal care items, e.g., toothbrushes, and the like; toys; small appliances; packaging; kitchen utensils; sports and leisure products; consumer electronics; PVC and silicone rubber replacement medical tubing; industrial hoses; and bath tubulars.

[0173] Polymerization process

[0174] The polymerization process to form the copolymers of the present disclosure (and subsequently the ionomers thereof) can be carried out in any suitable manner. Homogeneous, bulk, or solution phase polymerization processes can be used. These processes can be run in batch, semi-batch, or continuous mode. The polymerization process is typically a homogeneous polymerization process, which is defined as a process in which at least 90 wt% of the product is soluble in the reaction medium. Bulk homogeneous processes are particularly preferred. Bulk processes are defined as processes in which the monomer concentration in all feeds to the reactor is 70 vol% or greater. Alternatively, no solvent or diluent is present in or added to the reaction medium (except for small amounts used as a carrier for the catalyst system or other additives; e.g., propane in propylene; or amounts typically used in conjunction with the monomers; e.g., isoparaffins in propylene).

[0175] Suitable diluents / solvents for polymerization include non-coordinating, inert liquids. Examples include straight and branched-chain hydrocarbons such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and their isomers; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof such as ISOPAR TM ) available from ExxonMobil Chemical Co.; perhalogenated hydrocarbons such as perfluorinated C 4-10 alkanes, chlorobenzene, and aromatic and alkylsubstituted aromatic compounds, such as benzene, toluene, mesitylene, and xylenes. Suitable solvents also include liquid olefins which can act as monomers or comonomers including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof. In at least one embodiment, an aliphatic hydrocarbon solvent is used as the solvent, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and their isomers; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In another embodiment, the solvent is a non-aromatic solvent, such as aromatic compounds are present in the solvent in less than 1 wt%, such as less than 0.5 wt%, such as less than 0 wt%, based on the weight of the solvent.

[0176] In at least one embodiment, the feed concentration of monomers and comonomers for polymerization is 60 vol% solvent or less, such as 40 vol% or less, such as 20 vol% or less, based on the total volume of the feed stream. In at least one embodiment, the polymerization is run as a bulk process.

[0177] The polymerization can be run at any temperature and / or pressure suitable to obtain the desired polymer.

[0178] In some embodiments, hydrogen is present in the polymerization reactor at a partial pressure of 0.001 to 50 psig (0.007 to 345 kPa), for example, 0.01 to 25 psig (0.07 to 172 kPa), for example, 0.1 to 10 psig (0.7 to 70 kPa).

[0179] In at least one embodiment, the catalyst has an activity of at least 800 g polymer / g catalyst / hour, for example, 1,000 or more g polymer / g catalyst / hour, for example, 100 or more g polymer / g catalyst / hour, for example, 1,600 or more g polymer / g catalyst / hour.

[0180] In at least one embodiment, little or no scavenger is used in the process for making the copolymer. For example, the scavenger (e.g., trialkyl aluminum) can be present at zero mole percent, alternatively, the scavenger is present at a mole ratio of scavenger metal to transition metal of less than 100: 1, for example, less than 50: 1, for example, less than 15: 1, for example, less than 10: 1.

[0181] In at least one embodiment, the polymerization occurs in one reaction zone. A "reaction zone" is also referred to as a "polymerization zone" is a vessel in which polymerization takes place, for example, a batch reactor. When multiple reactors are used in series or in parallel configuration, each reactor is considered to be a separate polymerization zone. For multi-stage polymerization in both batch reactors and continuous reactors, each polymerization stage is considered to be a separate polymerization zone. In at least one embodiment, the polymerization occurs in one reaction zone.

[0182] The copolymers of the present disclosure can be made using a process in which monomers (such as linear alpha-olefins), metal-alkenyl compounds, optional comonomers, and optional dienes are contacted with a catalyst system comprising the combination product of an activator and a catalyst compound. The catalyst compound and activator can be combined in any order, and generally are combined prior to contact with the monomers, metal-alkenyl compounds, optional comonomers, and / or optional dienes.

[0183] In at least one embodiment, the process for making the copolymer can include using a suitable catalyst system to perform vinyl-addition polymerization between the alpha-olefins and the metal-alkenyl compounds. In at least one embodiment, the metal-alkenyl compound can be an alkenyl aluminum, an alkenyl borane, or any other suitable metal-alkenyl compound, such as those comprising a Group 13 metal.

[0184] In at least one embodiment, the metal alkenyl compound and solvent are mixed in a reactor. In at least one embodiment, the concentration of the metal alkenyl compound can be from about 0.001 mol% to about 20 mol%, for example, from about 0.001 mol% to about 10 mol%, for example, from about 0.01 mol% to about 5 mol%, based on the total moles of monomer, metal alkenyl compound, optional comonomer, and optional diene.

[0185] In at least one embodiment, the solvent can be selected from linear and branched hydrocarbons, cyclic and alicyclic hydrocarbons, perhalogenated hydrocarbons, aromatic and alkyl- substituted aromatic compounds, liquid olefins that can act as monomers or comonomers, aliphatic hydrocarbon solvents, and mixtures thereof.

[0186] In at least one embodiment, the reactor is equilibrated at a temperature of about 23 °C or greater, for example, from about 23 °C to about 190 °C, for example, from about 40 °C to about 100 °C, for example, from about 50 °C to about 90 °C, for example, from about 60 °C to about 80 °C, for example, from about 65 °C to about 75 °C, for example, about 70 °C.

[0187] In at least one embodiment, an alpha-olefin monomer is added to the mixture of metal alkenyl compound and solvent.

[0188] In at least one embodiment, one or more functionalization / quenching agents are added to the reactor. The functionalization / quenching agents can include CO2, CS2, COS, O2, H2O, SO2, SO3, P2O5, NO2, epoxides, cyclic anhydrides, maleic anhydride, methyl methacrylate, styrene, air, and the like.

[0189] In at least one embodiment, the concentration of the alpha-olefin monomer can be from about 50 mol% to about 99.9 mol%, for example, from about 60 mol% to about 99.9 mol%, for example, from about 70 mol% to about 99.9 mol%, for example, from about 80 mol% to about 99.5 mol%, for example, from about 85 mol% to about 99 mol%, for example, from about 90 mol% to about 99 mol%, for example, from about 93 mol% to about 99 mol%, for example, from about 95 mol% to about 99 mol%, based on the total moles of monomer, metal alkenyl compound, optional comonomer, and optional diene.

[0190] In at least one embodiment, the reactor is pressurized with a comonomer that is different from the alpha-olefin monomer. The comonomer can have any of the olefin compositions or other comonomer compositions provided herein.

[0191] In at least one embodiment, the concentration of the comonomer can be from about 1 mol% to about 99 mol%, for example, from about 5 mol% to about 40 mol%, for example, from about 10 mol% to about 35 mol%, for example, from about 15 mol% to about 30 mol%, for example, from about 20 mol% to about 30 mol%, for example, from about 25 mol% to about 30 mol%, based on the total moles of monomer, metal alkyl, optional comonomer, and optional diene.

[0192] The monomer and optional comonomer independently include substituted or unsubstituted C2to C 40 The α-olefin, for example, C2to C 20 The α-olefin, for example, C2to C 12 The α-olefin, for example, C2to C 40 The olefin, for example, C4to C 20 The olefin, for example, C6to C 12 The olefin. The C4to C 40 The olefin monomer can be linear, branched, or cyclic. The C4to C 40 The cyclic olefin can be strained or unstrained, monocyclic or polycyclic, and can optionally include a heteroatom and / or one or more functional groups. 40 The olefin, for example, C4to C 20 The olefin, for example, C6to C 12 The olefin. The C4to C 40 The olefin monomer can be linear, branched, or cyclic. The C4to C 40 The cyclic olefin can be strained or unstrained, monocyclic or polycyclic, and can optionally include a heteroatom and / or one or more functional groups.

[0193] Exemplary C2to C 40 The olefin monomer and optional comonomer can include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclododecene, 7-oxanorbornene, substituted derivatives thereof, and isomers thereof, such as hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, norbornene, and their respective homologs and derivatives, such as norbornene.

[0194] In at least one embodiment, the alpha-olefin monomer or comonomer can be a linear alpha-olefin. The linear alpha-olefin (LAO) can be a substituted or unsubstituted C6-C 60 LAO, e.g., C6-C 50 LAO, e.g., C8-C 40 LAO, e.g., C 10 -C 30 LAO, e.g., C 10 -C 20 LAO, e.g., C 15 -C 20 LAO, or C8-C 16 LAO, e.g., C8-C 12 LAO. In at least one embodiment, the copolymer has linear alpha-olefin units selected from the group consisting of 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, and combinations (one or more) thereof.

[0195] In at least one embodiment, a diene is optionally added to the reactant mixture. The addition of a diene to the copolymer can result in the formation of an ionomer with increased toughness compared to ionomers formed using similar polymers that do not contain diene units. In at least one embodiment, the diene can be a substituted or unsubstituted diene selected from the group consisting of C4-C 60 diene, e.g., C5-C 50 diene, e.g., C5-C 40 diene, e.g., C5-C 30 diene, e.g., C5-C 20 diene, e.g., C6-C 15 diene, e.g., C6-C 10dienes, such as C7-C9 dienes, for example, substituted or unsubstituted C7 dienes, C8 dienes, or C9 dienes. In at least one embodiment, the copolymer has diene units of C7 dienes. In at least one embodiment, the diene is a substituted or unsubstituted a,Ω-diene (e.g., the diene units of the copolymer are formed from di-vinyl monomers). The diene can be a linear di-vinyl monomer. In at least one embodiment, the diene is selected from butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, eicosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, and combinations (one or more) thereof. In some embodiments, the diene is selected from 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, and combinations (one or more) thereof. In at least one embodiment, the diene is selected from cyclopentadiene, vinyl norbornene, norbornadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, divinylbenzene, dicyclopentadiene, and combinations (one or more) thereof. In at least one embodiment, the ionic polymer has diene units of 5-ethylidene-2-norbornene.

[0196] In at least one embodiment, the concentration of optional diene added to the reaction mixture can be from about 0.1 mol% to about 40 mol%, for example, from about 0.1 mol% to about 20 mol%, for example, from about 1 mol% to about 10 mol%, based on the total moles of monomer, metal alkyl, optional comonomer, and diene, for example, from about 1 mol% to about 5 mol%. In some other embodiments, 500 ppm or less of diene is added to the polymerization, for example, 400 ppm or less, for example, 300 ppm or less. In other embodiments, at least 50 ppm of diene is added to the polymerization, or 100 ppm or more, or 150 ppm or more.

[0197] In at least one embodiment, the monomer, metal alkyl, optional comonomer, and optional diene are added to the reactor at a pressure independently selected from about 10 psig or more, for example, from about 10 psig to about 500 psig, for example, from about 50 psig to about 200 psig, for example, from about 80 psig to about 150 psig, for example, about 100 psig, or about 120 psig.

[0198] In at least one embodiment, the monomer alpha-olefin is ethylene or propylene.

[0199] In at least one embodiment, the alpha-olefin monomer is selected from the group consisting of C3-C 60 alpha-olefin, and the comonomer is ethylene.

[0200] In at least one embodiment, the alpha-olefin monomer is selected from the group consisting of C2and C4-C 60 alpha-olefin, and the comonomer is propylene. The addition of longer chain alpha-olefins to the copolymer can result in the formation of ionic polymers with untangled backbone for soft materials and better processing properties.

[0201] In at least one embodiment, the reaction mixture is rapidly stirred during polymerization.

[0202] In at least one embodiment, a suitable activator is dissolved in a hydrocarbon solvent such as hexane or toluene and added to the mixture. The activator can have any of the activator compositions provided herein.

[0203] In at least one embodiment, the polymerization is conducted for about 5 minutes or more, for example, about 5 minutes. to about 60 minutes, for example, about 5 minutes. to about 30 minutes, for example, about 10 minutes. to 20 minutes, for example, about 15 minutes.

[0204] In at least one embodiment, an oxidizing agent is added to the reactor. In at least one embodiment, the oxidizing agent can include CO2, CS2, COS, SO3, and combinations (one or more) thereof.

[0205] In at least one embodiment, the oxidizing agent is added to the reactor at a pressure of about 0.5 psig or more, for example, about 0.5 psig to about 500 psig, for example, about 50 psig to about 200 psig, for example, about 80 psig to about 150 psig, for example, about 100 psig.

[0206] In at least one embodiment, the oxidation is conducted at a reactor temperature of about 23 °C or more, for example, 23 °C to about 150 °C, for example, about 40 °C to about 100 °C, for example, about 50 °C to about 90 °C, for example, about 60 °C to about 80 °C, for example, about 65 °C to about 75 °C, for example, about 70 °C.

[0207] In at least one embodiment, the oxidation is conducted for about 5 minutes or more, for example, about 5 minutes. to about 60 minutes, for example, about 5 minutes. to about 30 minutes, for example, about 10 minutes. to 20 minutes, for example, about 15 minutes.

[0208] In at least one embodiment, the total reaction time is about 10 minutes. or more, for example, about 10 minutes. to about 60 minutes, for example, about 20 minutes. to about 40 minutes, for example, about 30 minutes.

[0209] Other additives can also be used in the polymerization, such as one or more scavengers, promoters, modifiers, chain transfer agents (e.g., diethyl zinc), reducing agents, oxidizing agents, hydrogen, aluminum alkyls, or silanes, as desired.

[0210] Useful chain transfer agents are typically alkylaluminoxanes, i.e., compounds represented by the formula AIR3, ZnR2(where each R is independently a Ci-C8aliphatic, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, or isomers thereof), or combinations thereof, such as diethyl zinc, methylaluminoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or combinations thereof.

[0211] Solution polymerization

[0212] In at least one embodiment, the polymerization process using the catalyst compounds of the present disclosure is a solution polymerization process.

[0213] Solution polymerization is a polymerization process in which the polymer is dissolved in a liquid phase polymerization medium, such as an inert solvent or monomer(s) or blends thereof. Solution polymerization is generally homogeneous. Homogeneous polymerization is polymerization in which the polymer product is dissolved in the polymerization medium. Such a system is not hazy, as described in J. Vladimir Oliveira et al. (2000) Ind. Eng, Chem. Res. v. 29, pg. 4627. Solution polymerization can involve polymerization in a continuous reactor in which the formed polymer, the supplied starting monomers, and catalyst materials are agitated to reduce or avoid concentration gradients, and in which the monomers act as diluents or solvents or in which a hydrocarbon is used as a diluent or solvent. Suitable processes can be operated at temperatures from about 0 °C to about 250 °C, such as from about 50 °C to about 170 °C, such as from about 80 °C to about 150 °C, such as from about 100 °C to about 140 °C, and / or at pressures of about 0.1 MPa or more, such as 2 MPa or more. The upper limit on pressure is not strictly bound, but generally can be about 200 MPa or less, such as 120 MPa or less, such as 30 MPa or less. Temperature control in the reactor generally can be obtained by balancing the heat of polymerization with reactor cooling with a reactor jacket or cooling coils that cool the reactor contents, self-cooling, pre-cooling of the feedstock, liquid medium (diluent, monomer, or solvent) evaporation, or a combination of all three. An adiabatic reactor with pre-cooled feed can also be used. The purity, type, and amount of solvent can be optimized for maximum catalyst productivity for a particular type of polymerization. Solvent can also be introduced as a catalyst carrier. Solvent can be introduced to the polymerization reactor in the gas phase or liquid phase, depending on the pressure and temperature. Advantageously, the solvent can be maintained in the liquid phase and introduced as a liquid. Solvent can be introduced in the feedstock to the polymerization reactor.

[0214] The processes described herein can be solution polymerization processes that can be conducted in a batch mode (e.g., batch; semi-batch) or in a continuous process. Suitable reactors can include kettle, loop, and tube designs. In at least one embodiment, the process is conducted in a continuous mode and a dual loop reactor in a series configuration is used. In at least one embodiment, the process is conducted in a continuous mode and a dual continuous stirred tank reactor (CSTR) in a series configuration is used. Further, the process can be conducted in a continuous mode and a tubular reactor can be used. In another embodiment, the process is conducted in a continuous mode and one loop reactor and one CSTR in a series configuration are used. The process can also be conducted in a batch mode and a single stirred tank reactor can be used.

[0215] Polymerization catalyst

[0216] Suitable polymerization catalysts can include any one or more of metallocenes, half- metallocenes, and post-metallocenes, as well as any other catalyst capable of introducing a metal ethylene, including bis(phenolate)heterocyclic Lewis base complexes. Suitable catalysts and catalyst systems are shown and described in US 9,796,795; WO 2017 / 192226; US 2020 / 0255555; US 2020 / 0254431; US 2020 / 0255556; WO 2020 / 167819; WO 2020 / 167824; and WO 2020 / 167838, which are incorporated herein by reference.

[0217] Useful metallocene catalyst compounds can be, for example, transition metal catalyst compounds having one, two, or three, typically one or two, substituted or unsubstituted cyclopentadienyl ligands (e.g., substituted or unsubstituted Cp, Ind, or Flu) bonded to the transition metal. Metallocene catalyst compounds as used herein include metallocenes containing Group 3 to 12 metal complexes, for example, Group 4 to 6 metal complexes, for example, Group 4 metal complexes.

[0218] The metallocene catalyst compound can be an unbridged or bridged metallocene catalyst compound represented by formula (MCN-I): A Cp B M'X' n or (MCN-II): A (T)Cp B M'X' n wherein each Cp A and Cp B is independently selected from cyclopentadienyl ligands (e.g., Cp, Ind, or Flu) and ligands isolobal to cyclopentadienyl, Cp A and Cp B one or both of which can contain a heteroatom, and Cp A and Cp Bone or both of which can be substituted with one or more R" groups; M' is selected from Group 3 to 12 atoms and Lanthanide series atoms; X' is an anionic leaving group; n is 0 or an integer from 1 to 4; each R" is independently selected from the group consisting of alkyl, substituted alkyl, heteroalkyl, alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, aryloxy, alkylthio, arylthio, aryl, substituted aryl, heteroaryl, aralkyl, aralkylidene, alkylaryl, alkylidenearyl, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocyclic, heteroaryl, heteroatom-containing group, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, silyl, boryl, phosphino, phosphine, amino, amine, ether, and thioether; (T) is a bridging group selected from the group consisting of divalent alkyl, divalent substituted alkyl, divalent heteroalkyl, divalent alkenyl, divalent substituted alkenyl, divalent heteroalkenyl, divalent alkynyl, divalent substituted alkynyl, divalent heteroalkynyl, divalent alkoxy, divalent aryloxy, divalent alkylthio, divalent arylthio, divalent aryl, divalent substituted aryl, divalent heteroaryl, divalent aralkyl, divalent aralkylidene, divalent alkylaryl, divalent alkylidenearyl, divalent haloalkyl, divalent haloalkenyl, divalent haloalkynyl, divalent heteroalkyl, divalent heterocyclic, divalent heteroaryl, divalent heteroatom-containing group, divalent hydrocarbyl, divalent substituted hydrocarbyl, divalent heterohydrocarbyl, divalent silyl, divalent boryl, divalent phosphino, divalent phosphine, divalent amino, divalent amine, divalent ether, and divalent thioether.

[0219] In at least one embodiment, Cp A and Cp Beach of R1and R2is independently selected from the group consisting of cyclopentadienyl, indenyl, fluorenyl, cyclopentaphenanthreneyl, benzindenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenanthrenindenyl, 3,4-benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopenta[a]acenaphthylenyl, 7-H-dibenzofluorenyl, indeno[1,2-9]anthracene, thienoindenyl, thienofluorenyl, and hydrogenated and substituted variations thereof, preferably cyclopentadienyl, n-propylcyclopentadienyl, indenyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, and n-butylcyclopentadienyl, 2-methyl-4-phenyl-1 H-indene, 2-methyl-7-phenyl-1 H-indene, 4-(4-(tert-butyl)phenyl)-2-methyl-1 H-indene, 7-(4-(tert-butyl)phenyl)-2-methyl-1 H-indene, 2-methyl-4-(o-tolyl)-1 H-indene, 2-methyl-7-(o-tolyl)-1 H-indene, 4-(3,5-dimethylphenyl)-2-methyl-1 H-indene, 7-(3,5-dimethylphenyl)-2-methyl-1 H-indene, 4-(3,5-di-tert-butylphenyl)-2-methyl-1 H-indene, 7-(3,5-di-tert-butylphenyl)-2-methyl-1 H-indene, 4-(3,5-di-tert-butyl-4-methoxyphenyl)-2-methyl-1 H-indene, 7-(3,5-di-tert-butyl-4-methoxyphenyl)-2-methyl-1 H-indene, 4-([1,1 '-biphenyl]-2-yl)-2-methyl-1 H-indene, 7-([1,1 '-biphenyl]-2-yl)-2-methyl-1 H-indene, 2-methyl-4-(2,4,5-trimethylphenyl)-1 H-indene, 2-methyl-7-(2,4,5-trimethylphenyl)-1 H-indene, 1 -(2-methyl-1 H-inden-4-yl)naphthalene, 1 -(2-methyl-1 H-inden-7-yl)naphthalene, 9-(2-methyl-1 H-inden-4-yl)anthracene, 9-(2-methyl-1 H-inden-7-yl)anthracene, 4-(3,5-bis(trifluoromethyl)phenyl)-2-methyl-1 H-indene, 7-(3,5-bis(trifluoromethyl)phenyl)-2-methyl-1 H-indene, 6-methyl-1,2,3,5-tetrahydro-s-indacene, 6-methyl-8-phenyl-1,2,3,5-tetrahydro-s-indacene, 6-methyl-4-phenyl-1,2,3,5-tetrahydro-s-indacene, 8-(4-(tert-butyl)phenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene, 4-(4-(tert-butyl)phenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene, 8-(2-5-tetrahydro-s-indacene, 6-methyl-4-(o-tolyl)-1,2,3,5-tetrahydro-s-indacene, 8-([1,1 '-biphenyl]-2-yl)-6-methyl-1,2,3,5-tetrahydro-s-indacene, 4-([1,1 '-biphenyl]-2-yl)-6-methyl-1,2,3,5-tetrahydro-s-indacene, 8-(3,5-di-tert-butyl-4-methoxyphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene, 4-(3,5-di-tert-butyl-4-methoxyphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene, 8-(3,5-di-tert-butylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene, 4-(3,5-di-tert-butylphenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene, 8-(3,5-bis(trifluoromethyl)phenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene, 4-(3,5-bis(trifluoromethyl)phenyl)-6-methyl-1,2,3,5-tetrahydro-s-indacene, 6-methyl-8-(naphthalen-1 -yl)-1,2,3,5-tetrahydro-s-indacene, 6-methyl-4-(naphthalen-1 -yl)-1,2,3,5-tetrahydro-s-indacene, 9-(6-methyl-1,2,3,7-tetrahydro-s-indacen-4-yl)anthracene, 9-(6-methyl-1,2,3,5-tetrahydro-s-indacen-4-yl)anthracene, 6-methyl-8-(2,4,5-trimethylphenyl)-1,2,3,5-tetrahydro-s-indacene, 4-methyl-8-(2,4,5-trimethylphenyl)-1,2,3,5-tetrahydro-s-indacene.

[0220] In at least one embodiment, each Cp A and Cp B may independently be an indacenyl group, a tetrahydroindenyl group, a tetrahydroindacenyl group.

[0221] In at least one embodiment, (T) is a bridging group containing at least one Group 13, 14, 15 or 16 element, especially boron or a Group 14, 15 or 16 element, preferably (T) is O, S, NR' or SiR'2, where each R' is independently hydrogen or a C1-C20 hydrocarbyl group. 20 hydrocarbyl group.

[0222] Other suitable polymerization catalysts for forming the alpha-olefin-metal alkyl and alpha-olefin-metal alkyl-diene copolymers provided herein can also include monocyclopentadienyl Group 4 transition metal compounds represented by the formula:

[0223] T y Cp' m MG n X q

[0224] wherein Cp' is a tetrahydroindenyl group (e.g., tetrahydro-s-indacenyl or tetrahydro-as- indacenyl) which can be substituted or unsubstituted, provided that when Cp' is tetrahydro-s- indacenyl:

[0225] 1) 3 and / or 4 positions are not aryl or substituted aryl,

[0226] 2) 3 position is not directly bonded to a group 15 or 16 heteroatom,

[0227] 3) there is no additional ring fused to the tetrahydroindenyl ligand,

[0228] 4) T is not bonded to the 2-position,

[0229] 5) 5, 6, or 7-position (e.g., 6-position) is geminally disubstituted, e.g., substituted with two C1-C6 alkyl groups; and, for example 10 6) when G is a tertiary butylamido, adamantylamido, cyclooctylamido, cyclohexylamido, or cyclododecylamido group, and the 5 and 7 positions are H, then the 6 position and / or X is not methyl;

[0230] 6) when G is a tertiary butylamido, adamantylamido, cyclooctylamido, cyclohexylamido, or cyclododecylamido group, and the 5 and 7 positions are H, then the 6 position and / or X is not methyl;

[0231] M is a group 3, 4, 5, or 6 transition metal, e.g., a group 4 transition metal, e.g., titanium, zirconium, or hafnium (e.g., titanium); G is a heteroatom group represented by the formula JR i z wherein J is N, P, O, or S, R i is a C1 to C 20 hydrocarbyl group, and z is 2-y when J is N or P, and z is 1-y when J is O or S (e.g., J is N and z is 1); T is a bridging group (e.g., a dialkylsilyl or dialkylcarbene group); T can be (CR 8 R 9 ) x , SiR 8 R 9 , or GeR 8 R 9 wherein x is 1 or 2, R 8 and R 9 are independently selected from substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl, and germylcarbyl groups, R 8 and R 9 may optionally be bonded together to form a ring structure, in one particular embodiment, R 8 and R 9is not an aryl group); y is 0 or 1, indicating the absence or presence of T; X is a leaving group (e.g., a halide, a hydride, an alkyl group, an alkenyl group, or an aralkyl group); m = 1; n = 1, 2, or 3; q = 1, 2, or 3; and the sum of m + n + q is equal to the oxidation state of the transition metal (e.g., 3, 4, 5, or 6, such as 4); for example, m = 1, n = 1, q is 2, and y = 1.

[0232] The catalyst system can include an activator and at least one metallocene catalyst compound, where the metallocene is a tetrahydroindenyl Group 4 transition metal compound, such as represented by the formula:

[0233] T y Cp' m MG n X q

[0234] where Cp' is a tetrahydroindenyl group (e.g., a tetrahydro-s-indenyl group or a tetrahydro-as-indenyl group) that can be substituted or unsubstituted, with the proviso that when Cp' is a tetrahydro-s-indenyl group:

[0235] 1) the 3 and / or 4 position is not an aryl or substituted aryl group,

[0236] 2) the 3 position is not directly bonded to a Group 15 or 16 heteroatom,

[0237] 3) there is no additional ring fused to the tetrahydroindenyl ligand,

[0238] 4) T is not bonded to the 2-position, and

[0239] 5) the 5, 6, or 7-position (e.g., the 6-position) is geminally disubstituted, such as substituted with two C1-C6alkyl groups; 10

[0240] M is a Group 3, 4, 5, or 6 transition metal, preferably a Group 4 transition metal, preferably titanium, zirconium, or hafnium (preferably titanium);

[0241] G is a heteroatom group represented by the formula JR i z where J is N, P, O, or S, R i is a C1to C 20 hydrocarbon group (or a C2to C 20 hydrocarbon group), and z is 2-y when J is N or P, and z is 1-y when J is O or S (e.g., J is N and z is 1);

[0242] T is a bridging group (e.g., a dialkylsilyl group or a dialkylcarbene group);

[0243] T is preferably a (CR 8 R​9 ) x , SiR 8 R 9 , or GeR 8 R 9 wherein x is 1 or 2, R 8 and R 9 are independently selected from substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl, and germylcarbyl groups, R 8 and R 9 may optionally be bonded together to form a ring structure, in a particular embodiment, R 8 and R 9 are not aryl groups);

[0244] y is 0 or 1, indicating that T is absent or present; X is a leaving group (e.g., a halide, a hydride, an alkyl group, an alkenyl group, or an aralkyl group);

[0245] m = 1; n = 1, 2, or 3; q = 1, 2, or 3; and the sum of m + n + q equals the oxidation state of the transition metal (e.g., 3, 4, 5, or 6, such as 4); for example, m = 1, n = 1, q is 2, and y = 1.

[0246] In some embodiments, the 6-position is not a methyl group.

[0247] In at least one embodiment, each R i is a linear, branched, or cyclic Ci to C 20 hydrocarbyl group, for example, independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof, for example, t-butyl and / or cyclododecyl.

[0248] In at least one embodiment, the mono-tetrahydro-s-indacenyl Group 4 transition metal compound is represented by Formula I or II:

[0249]

[0250] wherein:

[0251] M is a Group 4 metal (e.g., Hf, Ti, or Zr, such as Ti);

[0252] J is N, O, S, or P (e.g., N and p = 1);

[0253] p is 1 when J is N or P, and p is 0 when J is O or S;

[0254] each R a is independently a Ci-C 10 alkyl group (or a C2-C 10 alkyl group);

[0255] each Rc independently hydrogen or C1-C 10 alkyl;

[0256] each R 2 , R 3 , R 4 and R 7 independently are hydrogen, or C1-C 50 substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl, or germylcarbyl, provided that:

[0257] 1) R 3 and / or R 4 is not aryl or substituted aryl,

[0258] 2) R 3 is not directly bonded to a group 15 or 16 heteroatom, and

[0259] 3) adjacent R 4 , R c , R a or R 7 are not joined together to form a fused ring system;

[0260] each R' is independently C1-C 100 substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl, or germylcarbyl; T is (CR 8 R 9 ) x , SiR 8 R 9 or GeR 8 R 9 wherein x is 1 or 2, R 8 and R 9 are independently selected from substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl, and germylcarbyl, R 8 and R 9 may optionally be bonded together to form a ring structure;

[0261] each X is independently a leaving group, or two Xs are joined and bonded to the metal atom and bind to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene, provided that: in formula (I), when J(R')p is a tert-butylamino, adamantylamino, cyclooctylamino, cyclohexylamino, or cyclododecylamino group and R c is H, then R a and / or X is not methyl; and in formula (II), when JR' is a tert-butylamino, adamantylamino, cyclooctylamino, cyclohexylamino, or cyclododecylamino group and R c is H, then R aand / or X is not methyl.

[0262] R a is not methyl.

[0263] In at least one embodiment, the bridged mono-tetrahydro-as-indacene transition metal compound is represented by formula (III) or (IV):

[0264]

[0265] wherein:

[0266] M is a Group 3, 4, 5, or 6 transition metal;

[0267] B is the oxidation state of M and is 3, 4, 5, or 6;

[0268] c is B-2;

[0269] J is N, O, S, or P;

[0270] p is 2-y when J is N or P and p is 1-y when J is O or S;

[0271] each R 2 , R 3 , R 6 , and R 7 is independently hydrogen, or Ci-C 50 substituted or unsubstituted hydrocarbyl, halocarbyl, or silylcarbyl;

[0272] each R b and R c is independently Ci-C 10 alkyl or hydrogen;

[0273] each R' is independently Ci-C 100 substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl, or germylcarbyl;

[0274] T is (CR 8 R 9 ) x , SiR 8 R 9 , or GeR 8 R 9 wherein x is 1 or 2, R 8 and R 9 are independently selected from hydrogen, substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl, and germylcarbyl, R 8 and R 9 may optionally be bound together to form a ring structure;

[0275] y is 1 when T is present and 0 when T is absent;

[0276] each X is independently a leaving group, or two Xs are joined and bound to a metal atom and form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene.

[0277] In at least one embodiment, the bridged mono-tetrahydro-as-indacene-based transition metal compound is represented by formula A or B:

[0278]

[0279] wherein M, B, c, J, p, R 2 , R 3 , R 6 , R 7 , R', T, y, and X are as defined above for formula (III) and (IV), and each R b , R c , and R d is independently C1-C 10 alkyl or hydrogen, provided that two R b , two R c , or two R d are not hydrogen. In some embodiments, R d is independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof, such as hydrogen or methyl.

[0280] The present disclosure also relates to bridged mono-indacene-based Group 4 transition metal compounds represented by formula (V) or (VI):

[0281]

[0282] wherein:

[0283] M* is a Group 4 transition metal (e.g., Hf, Zr, or Ti);

[0284] J is N, O, S, or P (e.g., J is N and p is 1);

[0285] p is 2-y when J is N or P, and p is 1-y when J is O or S,

[0286] each R 2 , R 3 , R 6 , and R 7 is independently hydrogen or C1-C 50 substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl, or germylcarbyl;

[0287] each Rb and each R c independently is a C1-C 10 alkyl group or hydrogen;

[0288] each R' is independently a C1-C 100 substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl, or germylcarbyl group;

[0289] T is (CR 8 R 9 ) x , SiR 8 R 9 or GeR 8 R 9 where x is 1 or 2, R 8 and R 9 are independently selected from substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl, and germylcarbyl groups, R 8 and R 9 may optionally be bonded together to form a ring structure;

[0290] y is 1 when T is present, and y is 0 when T is not present;

[0291] each X is independently a leaving group, or two Xs are joined and bonded to the metal atom, and form a metallocycle ring, or two Xs are joined and bind to form a chelating ligand, a diene ligand, or an alkylidene.

[0292] In particularly useful embodiments of formula (V) and / or (VI), M* is a Group 4 metal (e.g., Hf, Zr, or Ti); J is nitrogen; each R 2 , R 3 , R 6 and R 7 are independently hydrogen or a C1-C 20 substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl, or germylcarbyl group; each R b and each R c is independently a C1-C 10 alkyl group (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or isomers thereof) or hydrogen; R' is a C1-C 20 substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl, or germylcarbyl group; T is (CR 8 R 9 ) x , SiR 8 R 9 or GeR 8 R 9 where x is 1 or 2, R 8 and R 9independently selected from substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl, and germylcarbyl radicals, y is 1, R 8 and R 9 may be optionally bound together to form a ring structure; each X is a halogen or C1-C 20 hydrocarbyl, wherein the hydrocarbyl groups are optionally joined to form a chelating ligand, a diene, or an alkylidene.

[0293] In at least one embodiment, M and / or M* is a Group 4 metal, such as titanium.

[0294] In at least one embodiment, R 3 is not substituted with a Group 15 or Group 16 heteroatom.

[0295] In at least one embodiment, each R 2 , R 3 , R 4 , R 6 , and R 7 is independently hydrogen, or a C1-C 50 substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl, or germylcarbyl radical, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl, or isomers thereof.

[0296] In at least one embodiment, each R a is independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof, such as methyl and ethyl, for example methyl.

[0297] Alternatively, the indacen ligand does not have a methyl group at the 6 position, or one or both R a is not a methyl group.

[0298] In at least one embodiment, R b is independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof, such as methyl and ethyl, for example methyl.

[0299] In at least one embodiment, R c is independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof, such as hydrogen or methyl.

[0300] In at least one embodiment, R' is a C1-C 100substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl, or germylcarbyl groups, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or isomers of, for example, tertiary butyl, neopentyl, cyclohexyl, cyclooctyl, cyclododecyl, adamantyl, or norbornyl.

[0301] In at least one embodiment, T is CR 8 R 9 , R 8 R 9 C-CR 8 R 9 , SiR 8 R 9 or GeR 8* R 9* wherein R 8 and R 9 are independently selected from substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl, and R 8 and R 9 may optionally be bonded together to form a ring structure, for example, each R 8 and R 9 is independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, benzyl, phenyl, methylphenyl, or isomers thereof, for example, methyl, ethyl, propyl, butyl, or hexyl.

[0302] In at least one embodiment, at least one of R 8 or R 9 is not aryl. In at least one embodiment, R 8 is not aryl. In at least one embodiment, R 9 is not aryl. In at least one embodiment, R 8 and R 9 are not aryl.

[0303] In at least one embodiment, R 8 and R 9 are independently C1-C 10 alkyl, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or isomers thereof.

[0304] In at least one embodiment, each R 2 , R 3 , R 4 and R 7 is independently hydrogen or a hydrocarbyl group. In at least one embodiment, each R 2 , R 3 , R 6 and R 7 is independently hydrogen or a hydrocarbyl group.

[0305] In at least one embodiment, each R 2 , R 3 , R 4 , and R 7 is independently hydrogen or a Ci-C 10 alkyl group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or isomers thereof.

[0306] In at least one embodiment, each R 2 , R 3 , R 6 , and R 7 is independently hydrogen or a Ci-C 10 alkyl group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or isomers thereof.

[0307] In at least one embodiment, R 2 is a Ci-C 10 alkyl group and R 3 , R 4 , and R 6 are hydrogen. In some embodiments, R 2 is a Ci-C 10 alkyl group and R 3 , R 6 , and R 7 are hydrogen.

[0308] In at least one embodiment, R 2 , R 3 , R 4 , and R 6 are hydrogen. In some embodiments, R 2 , R 3 , R 6 , and R 7 are hydrogen.

[0309] In at least one embodiment, R 2 is a methyl, ethyl, or an isomer of propyl, butyl, pentyl, or hexyl and R 3 , R 4 , and R 7 are hydrogen. In at least one embodiment, R 2 is a methyl, ethyl, or an isomer of propyl, butyl, pentyl, or hexyl and R 3 , R 6 , and R 7 are hydrogen.

[0310] In at least one embodiment, R 2 is a methyl and R 3 , R 4and R 7 is hydrogen. In some embodiments, R 2 is methyl and R 3 , R 6 and R 7 are hydrogen.

[0311] In at least one embodiment, R 3 is hydrogen. In at least one embodiment, R 2 is hydrogen. In at least one embodiment, R' is a C1-C 100 or C1-C 30 substituted or unsubstituted hydrocarbyl group.

[0312] In at least one embodiment, R' is a C1-C 30 substituted or unsubstituted alkyl (linear, branched, or cyclic), aryl, alkylaryl, or heterocyclic group.

[0313] In at least one embodiment, R' is a C1-C 30 linear, branched, or cyclic alkyl group. In at least one embodiment, R' is any isomer of methyl, ethyl, or propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl.

[0314] In at least one embodiment, R' is a cyclic or polycyclic hydrocarbyl group. In at least one embodiment, R' is selected from the group consisting of t-butyl, neopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, adamantyl, and norbornyl.

[0315] In at least one embodiment, R i is selected from the group consisting of t-butyl, neopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, adamantyl, and norbornyl.

[0316] In at least one embodiment, T is selected from the group consisting of diphenylmethylene, dimethylmethylene, 1,2-ethylene, cyclotrimethylene silylene, cyclotetramethylene silylene, cyclopentamethylene silylene, dimethylsilylene, diethylsilylene, methyl ethyl silylene, and dipropylsilylene.

[0317] In at least one embodiment, each R a is independently methyl, ethyl, propyl, butyl, pentyl, or hexyl.

[0318] In at least one embodiment, each R a is independently methyl or ethyl. In at least one embodiment, each R a is methyl.

[0319] In at least one embodiment, each R b is independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, or hexyl. In at least one embodiment, each R b is independently hydrogen, methyl, or ethyl. In at least one embodiment, each R c is methyl. b is independently hydrogen, methyl, or ethyl. In at least one embodiment, each R b is methyl.

[0320] In at least one embodiment, each X is a hydrocarbyl, halocarbyl, or substituted hydrocarbyl or halocarbyl group. In at least one embodiment, X is methyl, benzyl, or a halogen, wherein halogen includes fluorine, chlorine, bromine, and iodine.

[0321] In at least one embodiment of formula (I) or (II) described herein:

[0322] 1) R 3 and / or R 4 is not aryl or substituted aryl,

[0323] 2) R 3 is not directly bonded to a group 15 or 16 heteroatom, and

[0324] 3) adjacent R 4 , R c , R a , or R 7 are not joined together to form a fused ring system, and

[0325] 4) each R a is a C1-C 10 alkyl group (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or isomers thereof).

[0326] Useful catalysts also include compounds represented by formula (VII):

[0327] T y Cp' m MG n X q

[0328] wherein Cp' is a tetrahydroindacenyl group (e.g., tetrahydro-s-indacenyl or tetrahydro-as-indacenyl) that can be substituted or unsubstituted, provided that when Cp' is tetrahydro-s-indacenyl:

[0329] 1) 3 and / or 4 is not aryl or substituted aryl,

[0330] 2) 3 is not directly bonded to a group 15 or 16 heteroatom,

[0331] 3) no additional ring fused to the tetrahydroindenyl ligand,

[0332] 4) T is not bonded to the 2-position, and

[0333] 5) the 5, 6 or 7-position (e.g., the 6-position) is geminally disubstituted, e.g., substituted with two C1-C6alkyl groups; 10 alkyl groups;

[0334] M is a Group 3, 4, 5 or 6 transition metal, preferably a Group 4 transition metal, preferably titanium, zirconium or hafnium (preferably titanium);

[0335] G is a heteroatom group represented by the formula JR i z where J is N, P, O or S, R i is a C1to C 20 hydrocarbyl group, and z is 2-y when J is N or P, and z is 1-y when J is O or S (e.g., J is N and z is 1);

[0336] T is a bridging group (e.g., a dialkylsilyl or dialkylcarbene group); T is preferably (CR 8 R 9 ) x , SiR 8 R 9 or GeR 8 R 9 where x is 1 or 2, R 8 and R 9 are independently selected from substituted or unsubstituted hydrocarbyl, halocarbyl, silylcarbyl, and germylcarbyl groups, R 8 and R 9 may optionally be bonded together to form a ring structure, in one particular embodiment, R 8 and R 9 are not aryl groups);

[0337] y is 0 or 1, indicating the absence or presence of T;

[0338] X is a leaving group (e.g., a halide, hydride, alkyl, alkenyl, or aralkyl group);

[0339] m = 1; n = 1, 2 or 3; q = 1, 2 or 3; and the sum of m + n + q is equal to the oxidation state of the transition metal (e.g., 3, 4, 5 or 6, e.g., 4); for example, m = 1, n = 1, q is 2, and y = 1.

[0340] In at least one embodiment of the formula (VII) described herein, M is a Group 4 transition metal (e.g., Hf, Ti and / or Zr, e.g., Ti).

[0341] In at least one embodiment of formula (VII) described herein, J is N and R i is a linear, branched or cyclic hydrocarbon group containing 1 to 20 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or isomers thereof, including t-butyl, cyclododecyl, cyclooctyl, or isomers thereof), and z is 1 or 2, e.g., 1, and JR i z is cyclododecylamino, t-butylamino, and / or 1-adamantylamino.

[0342] In at least one embodiment of formula (VII) described herein, each X can be independently a halo, a hydride, an alkyl, an alkenyl, or an arylalkyl.

[0343] Alternatively, in at least one embodiment of formula (VII), each X is independently selected from the group consisting of a hydrocarbon group containing 1 to 20 carbon atoms, an aryl group, a hydride, an amide, an alkoxy, a sulfide, a phosphide, a halo, a diene, an amine, a phosphine, an ether, and combinations thereof (two Xs can form part of a fused ring or ring system), e.g., each X is independently selected from the group consisting of a halide, an aryl group, and a C1 to C5 alkyl group, e.g., each X is a phenyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or a chloro group.

[0344] In at least one embodiment of formula (VII) described herein, the Cp' group can be substituted with a combination of substituents R. Non-limiting examples of substituents R include one or more selected from the group consisting of hydrogen, or a linear, branched alkyl, or alkenyl, alkynyl, cycloalkyl, or aryl group, acyl, alkoxy, aryloxy, alkylthio, dialkylamino, alkoxycarbonyl, aryloxycarbonyl, aminocarbonyl, alkyl- or dialkyl-aminocarbonyl, acyloxy, acylamino, aryloylamino, linear, branched or cyclic alkylidene, or combinations thereof. In one embodiment, the substituents R have up to 50 non-hydrogen atoms, e.g., 1 to 30 carbons, which can also be substituted with halogen or heteroatoms, etc., provided that when Cp' is a tetrahydro-s-indacenyl group:

[0345] 1) the 3 and / or 4 position is not an aryl or substituted aryl group,

[0346] 2) the 3-position is not substituted with a Group 15 or 16 heteroatom,

[0347] 3) there is no additional ring fused to the tetrahydro-indacenyl ligand,

[0348] 4) T is not bonded to the 2-position, and

[0349] 5) the 5, 6, or 7-positions (e.g., the 6-position) are geminally disubstituted, e.g., substituted with two C1-C 10 alkyl groups.

[0350] Non-limiting examples of alkyl substituents R include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl, or phenyl groups, including all isomers thereof, e.g., t-butyl, isopropyl, etc. Other hydrocarbyl groups include fluoromethyl, fluoroethyl, difluoroethyl, iopropyl, bromohexyl, chlorobenzyl, and hydrocarbyl-substituted organometalloid radicals including trimethylsilyl, trimethylgermyl, methyldiethylsilyl, etc.; and halocarbyl-substituted organometalloid radicals including tris(trifluoromethyl)silyl, methyl-bis(difluoromethyl)silyl, bromomethyldimethylgermyl, etc.; and disubstituted boron radicals, including dimethylboron for example; disubstituted Group N, O, S, P radicals, including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine; chalcogen radicals including methoxy, ethoxy, propoxy, phenoxy, methylthio, and ethylthio. Non-hydrogen substituents R include atoms of carbon, silicon, boron, aluminum, nitrogen, phosphorous, oxygen, tin, sulfur, germanium, etc., including olefins, such as but not limited to olefinically unsaturated substituents, including vinyl-terminated ligands such as but-3-enyl, prop-2-enyl, hex-5-enyl, etc.

[0351] In at least one embodiment of formula (VII) described herein, the Cp' group, substituent(s) R are independently hydrocarbyl, heteroatom or heteroatom-containing groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or isomers thereof, N, O, S, P or C1to C12groups substituted with N, O, S and / or P heteroatoms or heteroatom-containing groups (typically having up to 12 atoms including N, O, S and P heteroatoms). 20 hydrocarbyl, provided that when Cp' is tetrahydro-s-indacenyl, the 3 and / or 4 position is not aryl or substituted aryl, the 3 position is not substituted with a Group 15 or 16 heteroatom, and there is no additional ring fused to the tetrahydro-indacenyl ligand, T is not bonded to the 2-position, and the 5, 6, or 7-position (e.g., the 6 position) is geminally disubstituted, e.g., with two C1-C12hydrocarbyl groups, and the 8, 9, or 10-position (e.g., the 9 position) is geminally disubstituted, e.g., with two C1-C12hydrocarbyl groups. 10 alkyl substituted.

[0352] In at least one embodiment of formula (VII), the Cp' group is a tetrahydro-as-indacenyl group which can be substituted.

[0353] In at least one embodiment of formula (VII), y is 1 and T is a bridging group containing at least one element from Group 13, 14, 15 or 16, in particular boron or a Group 14, 15 or 16 element. Examples of suitable bridging groups include P(=S)R*, P(=Se)R*, P(=O)R*, R*2C, R*2Si, R*2Ge, R*2CCR*2, R*2CCR*2CR*2, R*2CCR*2CR*2CR*2, R*C=CR*, R*C=CR*CR*2, R*2CCR* =CR*CR*2, R*C=CR*CR*=CR*, R*C=CR*CR*2CR*2, R*2CSiR*2, R*2SiSiR*2, R*2SiOSiR*2, R*2CSiR*2CR*2, R*2SiCR*2SiR*2, R*C=CR*SiR*2, R*2CGeR*2, R*2GeGeR*2, R*2CGeR*2CR*2, R*2GeCR*2GeR*2, R*2SiGeR*2, R*C=CR*GeR*2, R*B, R*2C-BR*, R*2C-BR*-CR*2, R*2C-O-CR*2, R*2CR*2C-O-CR*2CR*2, R*2C-O-CR*2CR*2, R*2C-O-CR*=CR*, R*2C-S-CR*2, R*2CR*2C-S-CR*2CR*2, R*2C-S-CR*2CR*2, R*2C-S-CR*=CR*, R*2C-Se-CR*2, R*2CR*2C-Se-CR*2CR*2, R*2C-Se-CR*2CR*2, R*2C-Se-CR*=CR*, R*2C-N=CR*, R*2C-NR*-CR*2, R*2C-NR*-CR*2CR*2, R*2C-NR*-CR*=CR*, R*2CR*2C-NR*-CR*2CR*2, R*2C-P=CR*, R*2C-PR*-CR*2, O, S, Se, Te, NR*, PR*, AsR*, SbR*, O-O, S-S, R*N-NR*, R*P-PR*, O-S, O-NR*, O-PR*, S-NR*, S-PR* and R*N-PR* where R* is hydrogen or a C 1- C 20hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl substituents, optionally two or more adjacent R* can join to form a substituted or unsubstituted, saturated, partially unsaturated, or aromatic, cyclic or polycyclic ring system. Examples of bridging groups T include CH2, CH2CH2, SiMe2, SiPh2, SiMePh, Si(CH2)3, Si(CH2)4, O, S, NPh, PPh, NMe, PMe, NEt, NPr, NBu, PEt, PPr, Me2SiOSiMe2, and PBu. In at least one embodiment, when Cp' is tetrahydro-s-indacenyl and T is R*2Si, then R* is not aryl.

[0354] In some embodiments, R* is not aryl or substituted aryl.

[0355] In some embodiments, T is represented by the formula ER d 2or (ER d 2)2, wherein E is C, Si, or Ge, and each R d is independently hydrogen, halogen, C1to C 20 hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), or C1to C 20 substituted hydrocarbyl, and two R d may form a cyclic structure comprising an aromatic, partially saturated, or saturated, cyclic or fused ring system. Preferably, T is a bridging group comprising carbon or silicon oxide, for example a dialkylsilyl group, for example T is selected from CH2, CH2CH2, C(CH3)2, SiMe2, cyclotrimethylidensilyl (Si(CH2)3), cyclopentamethylidensilyl (Si(CH2)5), and cyclotetramethylidensilyl (Si(CH2)4).

[0356] In some embodiments, R d is not aryl or substituted aryl.

[0357] Illustrative, but non-limiting examples of metallocenes for use in catalyst systems include:

[0358] dimethylsilyl(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1 -yl)(cyclooctylamido)M(R)2(e.g., TiCl2or TiMe2),

[0359] dimethylsilyl(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1 -yl)(cyclooctylamido)M(R)2(e.g., TiCl2or TiMe2),

[0360] Dimethylsilylene(6,6-dimethyl-l,5,6,7-tetrahydro-s-indacen-l-yl)(cyclo- dodecylamido)M(R)2(e.g., TiCl2or TiMe2),

[0361] Dimethylsilylene(6,6-dimethyl-l,5,6,7-tetrahydro-s-indacen-l-yl)(cyclo- dodecylamido)M(R)2(e.g., TiCl2or TiMe2),

[0362] Dimethylsilylene(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(cyclo- dodecylamido)M(R)2(e.g., TiCl2or TiMe2),

[0363] Dimethylsilylene(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(cyclo- dodecylamido)M(R)2(e.g., TiCl2or TiMe2),

[0364] Dimethylsilylene(7,7-dimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(cyclo- dodecylamido)M(R)2(e.g., TiCl2or TiMe2),

[0365] Dimethylsilylene(7,7-dimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(cyclo- dodecylamido)M(R)2(e.g., TiCl2or TiMe2),

[0366] μ-(CH3)2Si(2,6,6-trimethyl-l,5,6,7-tetrahydro-s-indacen-l-yl)(l-adamantyl- amino)M(R)2;

[0367] μ-(CH3)2Si(6,6-dimethyl-l,5,6,7-tetrahydro-s-indacen-l-yl)(l-adamantyl- amino)M(R)2;

[0368] μ-(CH3)2Si(2-methyl-6,6-diethyl-l,5,6,7-tetrahydro-s-indacen-l-yl)(l- adamantylamino)M(R)2;

[0369] μ-(CH3)2Si(6,6-diethyl-l,5,6,7-tetrahydro-s-indacen-l-yl)(l-adamantyl- amino)M(R)2;

[0370] μ-(CH3)2Si(2,7,7-trimethyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(l-adamantyl- amino)M(R)2;

[0371] μ-(CH3)2Si(2,6,6-trimethyl-l,5,6,7-tetrahydro-s-indacen-l-yl)(i-propylamino)M(R)2;

[0372] μ-(CH3)2Si(2,6,6-trimethyl-l,5,6,7-tetrahydro-s-indacen-l-yl)(i-propylamino)M(R)2;

[0373] μ-(CH3)2Si(2,6,6-trimethyl-l,5,6,7-tetrahydro-s-indacen-l-yl)(i-propylamino)M(R)2;

[0374] μ-(CH3)2Si(2,6,6-trimethyl-l,5,6,7-tetrahydro-s-indacen-l-yl)(i-propylamino)M(R)2;

[0375] μ-(CH3)2Si(2,6,6-trimethyl-l,5,6,7-tetrahydro-s-indacen-l-yl)(i-propylamino)M(R)2;

[0376] μ-(CH3)2Si(2,6,6-trimethyl-l,5,6,7-tetrahydro-s-indacen-l-yl)(i-propylamino)M(R)2;

[0377] μ-(CH3)2Si(2,6,6-trimethyl-l,5,6,7-tetrahydro-s-indacen-l-yl)(i-propylamino)M(R)2;

[0378] μ-(CH3)2Si(2,6,6-trimethyl-l,5,6,7-tetrahydro-s-indacen-l-yl)(i-propylamino)M(R)2;

[0379] μ-(CH3)2Si(2,6,6-trimethyl-l,5,6,7-tetrahydro-s-indacen-l-yl)(i-propylamino)M(R)2;

[0380] μ-(CH3)2Si(2,6,6-trimethyl-l,5,6,7-tetrahydro-s-indacen-l-yl)(i-propylamino)M(R)2;

[0381] μ-(CH3)2Si(2,6,6-trimethyl-l,5,6,7-tetrahydro-s-indacen-l-yl)(i-propylamino)M(R)2;

[0382] μ-(CH3)2Si(2,6,6-trimethyl-l,5,6,7-tetrahydro-s-indacen-l-yl)(i-propylamino)M(R)2;

[0383] μ-(CH3)2Si(2,6,6-trimethyl-l,5,6,7-tetrahydro-s-indacen- 1-yl)(cyclohexylamido)M(R)2;

[0384] μ-(CH3)2Si(2,6,6-trimethyl-l,5,6,7-tetrahydro-s-indacen- 1-yl)(cyclohexylamido)M(R)2;

[0385] μ-(CH3)2Si(2,6,6-trimethyl-l,5,6,7-tetrahydro-s-indacen- 1-yl)(cyclohexylamido)M(R)2;

[0386] μ-(CH3)2Si(2,6,6-trimethyl-l,5,6,7-tetrahydro-s-indacen- 1-yl)(cyclohexylamido)M(R)2;

[0387] μ-(CH3)2Si(2,6,6-trimethyl-l,5,6,7-tetrahydro-s-indacen- 1-yl)(cyclohexylamido)M(R)2;

[0388] μ-(CH3)2Si(2,6,6-trimethyl-l,5,6,7-tetrahydro-s-indacen- 1-yl)(cyclohexylamido)M(R)2;

[0389] μ-(CH3)2Si(2,6,6-trimethyl-l,5,6,7-tetrahydro-s-indacen- 1-yl)(cyclohexylamido)M(R)2;

[0390] μ-(CH3)2Si(2,6,6-trimethyl-l,5,6,7-tetrahydro-s-indacen- 1-yl)(cyclohexylamido)M(R)2;

[0391] μ-(CH3)2Si(2,6,6-trimethyl-l,5,6,7-tetrahydro-s-indacen- 1-yl)(cyclohexylamido)M(R)2;

[0392] μ-(CH3)2Si(2,6,6-trimethyl-l,5,6,7-tetrahydro-s-indacen- 1-yl)(cyclohexylamido)M(R)2;

[0393] μ-(CH2)3Si(2,6,6-trimethyl-l,5,6,7-tetrahydro-s-indacen- 1-yl)(cyclohexylamido)M(R)2;

[0394] μ-(CH2)4Si(2,6,6-trimethyl-l,5,6,7-tetrahydro-s-indacen- 1-yl)(cyclohexylamido)M(R)2;

[0395] μ-(CH2)5Si(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1 -yl)(t-butylamido)M(R)2;

[0396] μ-(CH3)2C(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1 -yl)(t-butylamido)M(R)2;

[0397] μ-(CH2)3Si(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1 -yl)(t-butylamido)M(R)2;

[0398] μ-(CH2)4Si(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1 -yl)(t-butylamido)M(R)2;

[0399] μ-(CH2)5Si(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1 -yl)(t-butylamido)M(R)2;

[0400] μ-(CH3)2C(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1 -yl)(t-butylamido)M(R)2; and

[0401] μ-(CH3)2Si(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1 -yl)(neopentylamido)M(R)2;

[0402] wherein M is selected from the group consisting of Ti, Zr, and Hf, and R is selected from halogen or Ci to C5 alkyl, for example R is methyl or a halogen group (e.g., TiCl2or TiMe2), provided however, that when the compound is dimethylsilylene(2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1 -yl)(Z)Ti(R)2or μ-(CH3)2Si(2-methyl-3,6,7,8-tetrahydro-as-indacen-3-yl)(Z)Ti(R)2, wherein Z is t-butylamido, adamantylamido, cyclooctylamido, cyclohexylamido, or cyclododecylamido, then R is not methyl.

[0403] In at least one embodiment, the catalyst system comprises μ-(CH3)2Si(η5-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1 -yl)(t-butylamido)M(R)2; wherein M is selected from the group consisting of Ti, Zr, and Hf, and R is selected from halogen or Ci to C5 alkyl, for example, R is methyl. In one embodiment, M is Ti and R is Cl, Br, or Me.

[0404] In alternative embodiments, two or more different transition metal compounds can be used herein. For purposes of the present disclosure, two transition metal compounds are considered different if they differ by at least one atom. For example, "Me2Si(2,7,7-Me3-3,6,7,8-tetrahydro-as-indacen-3-yl)(cyclohexylamido)TiCl2" is different from "Me2Si(2,7,7-Me3-3,6,7,8-tetrahydro-as-indacen-3-yl)(n-butylamido)TiCl2", which is different from Me2Si(2,7,7-Me3-3,6,7,8-tetrahydro-as-indacen-3-yl)(butylamido)HfCl2.

[0405] In at least one embodiment, a mono-tetrahydroindenyl compound described herein is used in the catalyst system.

[0406] Particularly useful catalyst compounds in the present invention include those represented by one or more of the complexes of Figure 5A 、 5B 5C, 5D, and 5E.

[0407] Activators

[0408] The terms "cocatalyst" and "activator" are used interchangeably herein and are defined to be any compound which activates any of the aforementioned catalyst compounds by converting the neutral catalyst compound into a catalytically active catalyst compound cation together with the counterion. Non-limiting activators include, for example, aluminoxanes, alkylaluminum compounds, ionizing activators (which can be neutral or ionic), and conventional types of cocatalysts. Activators typically include aluminoxane compounds, modified aluminoxane compounds, and ionizing anion precursor compounds which abstract a reactive, sigma-bonded metal ligand, thereby ionizing the metal complex and providing a charge-balancing, non-coordinating or weakly coordinating anion.

[0409] Aluminoxane activators

[0410] Aluminoxane activators are used as activators in the catalyst systems described herein. Aluminoxanes are generally oligomeric compounds containing -Al(R 1 )-O- subunits, where R 1is an alkyl group. Examples of aluminoxanes include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, and isobutylaluminoxane. Alkylaluminoxanes and modified alkylaluminoxanes are suitable as catalyst activators, especially when the abstractable ligand is an alkyl, halo, alkoxy, or amino group. Mixtures of different aluminoxanes and modified aluminoxanes can also be used. It can be preferred to use a visually clear methylaluminoxane. Cloudy or gelled aluminoxanes can be filtered to make a clear solution or the clear aluminoxane can be decanted from the cloudy solution. A useful aluminoxane is modified methylaluminoxane (MMAO) cocatalyst 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methyl Aluminoxane 3A, covered by patent number U.S. Patent No. 5,041,584).

[0411] When the activator is an aluminoxane (modified or unmodified), some embodiments select a maximum activator dose of up to 5000-fold molar excess (Al / M) relative to the catalyst compound (per metal catalytic site). The minimum activator to catalyst compound ratio is a 1 : 1 molar ratio. Alternative ranges include 1 : 1 to 500: 1, or 1 : 1 to 200: 1, or 1 : 1 to 100: 1, or 1 : 1 to 50: 1.

[0412] Non-coordinating anion activators

[0413] Non-coordinating anion activators can also be used herein. The term "non- coordinating anion" (NCA) means an anion that does not coordinate to the cation or coordinates only weakly, thereby remaining sufficiently unstablized to be displaced by a neutral Lewis base. "Compatible" non-coordinating anions are those which do not degrade upon isolation of the complex, do not decompose upon formation of the complex, and do not transfer an anionic fragment to the cation that facilitates decomposition of the complex. Further, the anion does not transfer an anionic substituent or fragment to the cation that facilitates decomposition of the complex to neutral transition metal compounds and neutral by-products from the anion. Non-coordinating anions useful according to the present disclosure are those that are compatible with the catalysts of the present disclosure, that stabilize the catalysts in the +1 oxidation state, and that remain sufficiently unstablized to be displaced by a neutral Lewis base in the polymerization process.

[0414] It is within the scope of the present disclosure to use ionizing or stoichiometric activators (neutral or ionic) in combination with aluminoxane or modified aluminoxane activators, such as tris(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, trisperfluorophenyl boron metalloid precursor, or trisperfluoronaphthyl boron metalloid precursor, polyhalogenated heteroborane anions (WO 1998 / 043983), boronic acids (U.S. Patent No. 5,942,459). The use of neutral or ionic activators in combination with the aluminoxane or modified aluminoxane activators is also within the scope of the present disclosure.

[0415] The catalyst system of the present disclosure can include at least one non-coordinating anion (NCA) activator. In particular, the catalyst system can include an NCA that does not coordinate, or only weakly coordinates, with the cation, thereby remaining sufficiently labile to be displaced during polymerization.

[0416] The terms "cocatalyst" and "activator" are used interchangeably herein and are defined to be any compound, which is capable of activating any of the aforementioned catalyst compounds by converting the neutral catalyst compound to a catalytically active catalyst compound cation.

[0417] In at least one embodiment, a boron-containing NCA activator represented by the formula:

[0418] Zd+(Ad-)

[0419] wherein: Z is (L-H) or a reducible Lewis acid, L is a neutral Lewis base; H is hydrogen; (L-H) is a Bronsted acid; A d- is a boron-containing non-coordinating anion having the charge d-; d is 1, 2, or 3.

[0420] Cationic Component Z d + may include a Bronsted acid, such as a proton or a protonated Lewis base or a reducible Lewis acid capable of protonating or abstracting a moiety, such as an alkyl or aryl proton, from the bulky ligand metallocene-containing transition metal catalyst precursor to yield a cationic transition metal species.

[0421] Activating Cation Z d + may also be a moiety such as silver, (tropyllium), ferrocenium and mixtures, such as carbon and ferrocenium such as Z d + is triphenylcarbenium The reducible Lewis acid can be any triarylcarbenium (wherein the aryl groups can be substituted or un-substituted, such as those represented by the formula (Ar3C+), wherein Ar is an aryl group or an aryl group substituted with a heteroatom, a C1-C20 40 alkyl group or a substituted C1-C20 40 alkyl group), for example, the reducible Lewis acids for "Z" in formula (14) above include those represented by the formula (Ph3C), wherein Ph is a substituted or un-substituted phenyl group, such as substituted with a C1to C20 40 alkyl group or a substituted C1to C20 40 alkyl group, such as a C1to C2020 alkyl or aromatic groups or substituted C1 to C 20 alkyl or aromatic groups, for example Z is triphenylcarbenium

[0422] when Z d + is an activated cation (L-H) d + when it is a Brønsted acid, capable of donating a proton to a transition metal catalytic precursor, thereby generating a transition metal cation, including ammonium, oxonium silyl and mixtures thereof, for example ammonium from methylamine, aniline, dimethylamine, diethylamine, N-methylanilinium, diphenylamine, trimethylamine, triethylamine, N,N-dimethylanilinium, methyldiphenylamine, pyridinium, p-bromo N,N-dimethylanilinium, p-nitro-N,N-dimethylanilinium, sulfonium from triethylphosphonium, triphenylphosphonium, and diphenylphosphonium. oxonium from ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, and dioxane. sulfonium from sulfides such as diethyl sulfide, tetrahydrothiophene, and mixtures thereof. sulfonium from sulfides such as diethyl sulfide, tetrahydrothiophene, and mixtures thereof.

[0423] anionic component A d- including those having the formula [M k+ Q n ] d- wherein k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6 (e.g., 1, 2, 3, or 4); n-k = d; M is an element selected from Group 13 of the Periodic Table of the Elements, e.g., boron or aluminum, and Q is independently a hydride, a bridged or unbridged dialkylamide, a halide, an alkoxy, an aryloxy, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, a substituted halocarbyl, and a halogenated hydrocarbyl radical, said Q having up to 20 carbon atoms, with the proviso that in not more than one occurrence Q is a halide. Preferably, each Q is a fluorinated hydrocarbyl having 1 to 20 carbon atoms, preferably each Q is a fluorinated aryl, e.g., each Q is a pentafluoroaryl. Suitable A d- Examples of A

[0424] Illustrative, but non-limiting examples of boron compounds that can be used as activating co-catalysts are those described in US 8,658,556 as activators (especially those listed as activators specifically), which is incorporated herein by reference.

[0425] For example, ionic stoichiometric activators Z d + (A d-) is one or more of the following: tetra(perfluorophenyl)boron N,N-dimethylanilinium, tetra(perfluoronaphthyl)boron N,N-dimethylanilinium, tetra(perfluorobiphenyl)boron N,N-dimethylanilinium, tetra(3,5-bis(trifluoromethyl)phenyl)boron N,N-dimethylanilinium, tetra(perfluoronaphthyl)boron triphenylcarbenium tetra(perfluorobiphenyl)boron triphenylcarbenium tetra(3,5-bis(trifluoromethyl)phenyl)boron triphenylcarbenium or tetra(perfluorophenyl)boron triphenylcarbenium

[0426] A bulky activator can also be used as the NCA here. As used here, "bulky activator" means an anion activator represented by the formula:

[0427]

[0428] wherein: each R1is independently a halo group, such as a fluoro group; Ar is a substituted or unsubstituted aryl group (e.g., a substituted or unsubstituted phenyl group), such as a phenyl group substituted with C1-C 40 hydrocarbyl groups, such as C1-C 20 alkyl or aromatic groups; each R2is independently a halo group, a C6-C 20 substituted aromatic hydrocarbyl group, or a siloxy group of the formula -O-Si-R a , where R a is a C1-C 20 hydrocarbyl group or a hydrocarbylsilyl group (e.g., R2is a fluoro group or a perfluorinated phenyl group); each R3is a halo group, a C6-C 20 substituted aromatic hydrocarbyl group, or a siloxy group of the formula -O-Si-R a , where R a is a C1-C 20 hydrocarbyl group or a hydrocarbylsilyl group (e.g., R3is a fluoro group or a C6perfluorinated aromatic hydrocarbyl group); wherein R2and R3may form one or more saturated or unsaturated substituted or unsubstituted rings (e.g., R2and R3form a perfluorinated phenyl ring); and L is a neutral Lewis base; (L-H)+is a Bronsted acid; d is 1, 2, or 3; wherein the anion has a molecular weight greater than 1,020 g / mol; wherein at least three of the substituents on the B atom each have a molecular volume greater than or greater than or greater than .

[0429] for example, (Ar3C) d + is (Ph3C) d + , where Ph is a substituted or unsubstituted phenyl group, such as a phenyl group substituted with C1-C40 Hydrocarbon group or substituted C1-C 40 Hydrocarbon groups, for example, C1-C 20 Alkyl or aromatic or substituted C1-C 20 Alkyl or aromatic groups.

[0430] "Molecular volume" is used here as an approximation of the three-dimensional volume of an activator molecule in solution. The comparison of substituents with different molecular volumes allows us to consider a substituent with a smaller molecular volume as "not too large" compared to a substituent with a larger molecular volume. Conversely, a substituent with a larger molecular volume can be considered as "larger" compared to a substituent with a smaller molecular volume.

[0431] Molecular volume can be calculated as reported in "A Simple 'Back of the Envelope' Method for Estimating the Densities and Molecular Volumes of Liquids and Solids," Journal of Chemical Education, v.71(11), November 1994, pp.962-964. Molecular volume (MV) (unit: Calculate using the following formula: MV = 8.3V s V s It's scaling the volume. V s It is the sum of the relative volumes of the constituent atoms, and is calculated from the molecular formula of the substituents using the relative volumes in the table below. For fused rings, V s Reduced by 7.5% per fused ring.

[0432] Element Relative volume H 1 First short period, Li to F 2 Second short period, Na to Cl 4 First long period, K to Br 5 Second long period, Rb to I 7.5 Third long period, Cs to Bi 9

[0433] For a list of particularly useful bulk activators, see US 8,658,556, which is incorporated herein by reference.

[0434] In another embodiment, one or more of the NCA activators are selected from the activators described in US 6,211,105.

[0435] Activators may include N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate, N,N-dimethylphenylammonium tetra(perfluoronaphthyl)borate, N,N-dimethylphenylammonium tetra(perfluorobiphenyl)borate, N,N-dimethylphenylammonium tetra(perfluorophenyl)borate, N,N-dimethylphenylammonium tetra(3,5-bis(trifluoromethyl)phenyl)borate, and triphenylcarbon tetra(perfluoronaphthyl)borate. Triphenylcarbon tetra(perfluorobiphenyl)boronic acid triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate triphenylcarbenium tetrakis(perfluoronaphthyl)borate [Ph3C + ][B(C6F5)4 - ]; [Me3NH + ][B(C6F5)4 - ]; 1 -(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidine and triphenylcarbenium tetrakis(pentafluorophenyl)borate, 4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

[0436] In at least one embodiment, the activator comprises a triarylcarbenium (e.g. tripotassium tetrakis(pentafluorophenyl)borate triphenylcarbenium tetrakis(pentafluorophenyl)borate triphenylcarbenium tetrakis(2,3,4,6-tetrafluorophenyl)borate triphenylcarbenium tetrakis(perfluoronaphthyl)borate triphenylcarbenium tetrakis(perfluorobiphenyl)borate triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate ).

[0437] In another embodiment, the activator comprises one or more of: trialkylammonium tetrakis(pentafluorophenyl)borate, N,N-dialkylbenzenaminium tetrakis(pentafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylbenzenaminium) tetrakis(pentafluorophenyl)borate, trialkylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, N,N-dialkylbenzenaminium tetrakis(2,3,4,6-tetrafluorophenyl)borate, trialkylammonium tetrakis(perfluoronaphthyl)borate, N,N-dialkylbenzenaminium tetrakis(perfluoronaphthyl)borate, trialkylammonium tetrakis(perfluorobiphenyl)borate, N,N-dialkylbenzenaminium tetrakis(perfluorobiphenyl)borate, trialkylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkylbenzenaminium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethyl-(2,4,6-trimethylbenzenaminium) tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di(isopropyl)ammonium tetrakis(pentafluorophenyl)borate, (wherein alkyl is methyl, ethyl, propyl, n-butyl, sec-butyl or t-butyl).

[0438] A typical NCA activator to catalyst ratio, for example, all NCA activator to catalyst ratio is a molar ratio of about 1 : 1. Alternative ranges include 0.1 : 1 to 100: 1, or 0.5: 1 to 200: 1, or 1 : 1 to 500: 1, or 1 : 1 to 1000: 1. Especially useful ranges are 0.5: 1 to 10: 1, for example 1 : 1 to 5: 1.

[0439] Useful activators herein also include those described in US 7,247,687 at column 169, line 50 to column 174, line 43, and especially at column 172, line 24 to column 173, line 53.

[0440] It is within the scope of the present disclosure that the catalyst compound can be combined with a combination of aluminoxane and NCA (see, for example, US 5,153,157, US 5,453,410, EP 0 573 120 Bl, WO 1994 / 007928, and WO 95 / 14044, which discuss the use of aluminoxane in combination with ionizing activators).

[0441] Experimental Section

[0442] The foregoing discussion can be further described with reference to the following non-limiting examples, wherein the test procedures are as described below.

[0443] Test Methods

[0444] Due to strong ion clustering, ionomers are generally insoluble in any solvent. The molecular weight fraction of the metal-olefin containing copolymer is determined by acidifying the ionomers to make them soluble in trichlorobenzene (TCB). Thereafter, the acidified copolymer is subjected to gel permeation chromatography (GPC) to measure the molecular weight fraction. For the purposes of the present invention and the appended claims, the molecular weight fraction of the acidified polymer shall be considered to be the molecular weight fraction of the polymer prior to acidification.

[0445] 4D Gel Permeation Chromatography: Unless otherwise indicated, distributions and fractions of molecular weight (Mw, Mn, Mz, Mw / Mn, etc.), comonomer content, and branching index (g') are determined by using a high temperature gel permeation chromatograph (Polymer Char GPC-IR) equipped with a multiple channel band filter based infrared detector IR5 (having a 30 channels / cm band width) and a 3-angle laser light scattering detector. The high temperature GPC is equipped with an on-line solvent degassing device and an autosampler. The system is equipped with an on-line differential refractometer (dRI) and a right angle light scattering (RALS) detector from Wyatt Technology Corporation. The system is further equipped with a multiple channel 20 angle light scattering (MALS) detector from Wyatt Technology Corporation. The system is controlled by ASTRA software version 4.6.2.3. The system is further equipped with a high performance GPC cleaner (Automated Sample Handler) from Polymer Char. -1 to about 3,000 cm -1a multi-channel bandpass filter-based infrared detector assembly IR5), an 18-angle light scattering detector, and a viscometer. Three Agilent PLgel 10 pm Mixed-B LS columns were used to provide polymer separation. Reagent grade 1,2,4-trichlorobenzene (TCB) from Sigma-Aldrich containing ~300 ppm antioxidant BHT can be used as the mobile phase which can be operated at a nominal flow rate of ~1 mL / min and a nominal injection volume of ~200 μL. The entire system including transfer lines, columns, and detectors can be contained in an oven maintained at ~145°C. A given amount of sample can be weighed and sealed in a standard vial to which ~10 μL of flow marker (heptane) can be added. After loading the vial into the autosampler, the oligomer or polymer can be automatically dissolved in the instrument using ~8 mL of added TCB solvent at ~160°C under continuous shaking. The sample solution concentration can be ~0.2 to ~2.0 mg / ml, with lower concentrations being used for higher molecular weight samples. The concentration c at each point in the chromatogram can be calculated from the IR5 broadband signal I minus baseline using the following equation: c = aI, where a is a mass constant determined with polyethylene or polypropylene standards. Mass recovery can be calculated from the integrated area of the concentration chromatogram over elution volume and the proportion of injected mass which is equal to the pre-determined concentration multiplied by the injection loop volume. The conventional molecular weight (IR MW) can be determined by combining a universal calibration relationship with column calibration performed with a series of monodispersed polystyrene (PS) standards ranging from 700 to 10M gm / mole. The MW at each elution volume is calculated using the following equation:

[0446]

[0447] where the variables with subscript "PS" represent polystyrene and those without a subscript represent the sample under test. In this method, a = 0.67 and K = 0.000175, and a and K for other materials are calculated by the GPC ONE PS PS TM 2019f software (Polymer Characterization, S.A., Valencia, Spain). Unless otherwise noted, concentrations are expressed in g / cm 3 , molecular weights are expressed in g / mole, and intrinsic viscosities (and thus the K in the Mark-Houwink equation) are expressed in dL / g.

[0448] ​​The comonomer composition is determined from the ratio of the IR5 detector intensities corresponding to the CH2and CH3channels calibrated with a series of PE and PP homopolymer / copolymer standards whose nominal values were previously determined by NMR or FTIR. In particular, this provides the methyl groups per 1,000 total carbons (CH3 / 1000TC) as a function of molecular weight. The short chain branching (SCB) content per 1,000 TC (SCB / 1000TC) as a function of molecular weight is then calculated by applying a chain end correction to the CH3 / 1000TC functionality, assuming each chain to be linear and terminated by a methyl group at each end. The weight % comonomer is then obtained from the following expression, where f is 0.3, 0.4, 0.6, 0.8, etc. for C3, C4, C6, C8, etc. comonomers, respectively:

[0449] w2 = f * SCB / 1000TC.

[0450] The bulk composition of the polymer from GPC-IR and GPC-4D analysis is obtained by considering the total signal of the CH3and CH2channels between the integration limits of the concentration chromatogram. First, the following ratios are obtained

[0451]

[0452] The same calibration of the CH3and CH2signal ratio is then applied (as mentioned previously in obtaining CH3 / 1000TC as a function of molecular weight) to obtain the bulk CH3 / 1000TC. The bulk methyl chain ends per 1000 TC (bulk CH3ends / 1000TC) are obtained by a weighted average of the chain end correction over the molecular weight range. Then

[0453] w2b = f * bulk CH3 / 1000TC

[0454] The bulk SCB / 1000TC = bulk CH3 / 1000TC - bulk CH3ends / 1000TC and the bulk SCB / 1000TC is converted to the bulk w2 in the same way as described above.

[0455] The LS detector is an 18-angle Wyatt Technology High Temperature DAWN HELEOS II. The LS molecular weight (M) at each point of the chromatogram is determined by analyzing the LS output values using the Zimm model for static light scattering (Light Scattering from Polymer Solutions; Huglin, M. B., Ed.; Academic Press, 1972.):

[0456]

[0457] where AR(0) is the excess Rayleigh scattering intensity measured at scattering angle 0, c is the polymer concentration determined from the IR5 analysis, A2 is the second virial coefficient, P(0) is the form factor for a monodisperse random coil, K o is the optical constant of the system:

[0458]

[0459] where N A is Avogadro's number, (dn / dc) is the refractive index increment of the system, n = 1.500 for TCB at 145°C, and l = 665 nm. For the analysis of polyethylene homopolymer, ethylene-hexene copolymer, and ethylene-octene copolymer, dn / dc = 0.1048 ml / mg and A2 = 0.0015; for the analysis of ethylene-butene copolymer, dn / dc = 0.1048 x (1 - 0.00126 x w2) ml / mg and A2 = 0.0015, where w2 is the weight percent of butene comonomer.

[0460] Specific viscosity is determined using a high temperature Agilent (or Viscotek Corporation) viscometer with four capillaries arranged in a Wheatstone bridge configuration and two pressure transducers. One measures the total pressure drop across the detector, the other the differential pressure between the two sides of the bridge. The specific viscosity, h s is calculated from their outputs. The intrinsic viscosity, [h], at each point in the chromatogram is calculated from the following equation: [h] = h s / c, where c is the concentration and determined from the IR5 broadband channel output. The viscosity, Mw, at each point is calculated as where a ps = 0.67, K PS = 0.000175.

[0461] The branching index, g' vis , is calculated from the output of the GPC-IR5-LS-VIS method as follows. The average intrinsic viscosity, [h] 平均 of the sample is calculated as follows:

[0462]

[0463] where the sum is taken over all chromatogram slices, i, between the integration limits. The branching index, g' vis , is defined as: where Mv is the weight average molecular weight based on the molecular weight determined by LS analysis, and K and a for a reference linear polymer are determined by GPC ONE TM2019f software (Polymer Characterization, S.A., Valencia, Spain). Concentrations are reported in g / cm3unless otherwise noted. 3 indicates the molecular weight is expressed in g / mole, and the intrinsic viscosity (and thus K in the Mark-Houwink equation) is expressed in dL / g. The calculation of w2b values is as discussed above.

[0464] Differential Scanning Calorimetry (DSC)

[0465] Crystallization temperature (Tc) and melting temperature (or melting point, Tm) are measured using differential scanning calorimetry (DSC) on a commercially available instrument, such as a TA Instruments 2920 DSC or TA Instruments 2900 DSC. Typically, 6-10 mg of molded polymer or plasticized polymer is encapsulated in an aluminum pan and loaded into the instrument at room temperature. Melting data (first heat) is acquired by heating the sample at a heating rate of 10 °C / min to at least 30 °C above its melting temperature (typically 200 °C for polypropylene). The sample is kept at that temperature for at least 5 minutes to destroy its thermal history. Crystallization data is obtained by cooling the sample from the melt at a cooling rate of 10 °C / min to at least 50 °C below its crystallization temperature. The sample is kept at that temperature for at least 5 minutes, and finally heated at 10 °C / min to acquire additional melting data (second heat). The endothermic melting transitions (first and second heats) and exothermic crystallization transitions are analyzed according to standard procedures. The reported melting temperature is the peak melting temperature from the second heat unless otherwise specified. For Tg determinations herein, a DSC 2500™ (TA Instruments™) is used with a heating rate of 10 °C / min from -150 °C to 150 °C.

[0466] For polymers showing multiple peaks, the melting temperature is defined as the peak melting temperature from the melting trace associated with the largest endothermic heat response (as opposed to the peak occurring at the highest temperature). Likewise, the crystallization temperature is defined as the peak crystallization temperature from the crystallization trace associated with the largest exothermic heat response (as opposed to the peak occurring at the highest temperature).

[0467] The area under the DSC curve is used to determine the heat of transition (enthalpy of fusion, Hf, upon melting), which can be used to calculate the degree of crystallinity (also referred to as percent crystallinity). The percent crystallinity (X%) is calculated using the following formula: [area under curve (in J / g) / H° (in J / g)] x 100, where H° is the ideal heat of fusion for a perfect crystal of the homopolymer of the major monomer component. o is the ideal heat of fusion for a perfect crystal of the homopolymer of the major monomer component. H° oThese values are obtained from the Polymer Handbook, Fourth Edition, published by John Wiley and Sons, New York 1999, except that a value of 290 J / g is used for H o (polyethylene), a value of 140 J / g is used for H o (polybutylene), a value of 207 J / g is used for H o (polypropylene).

[0468] 1 H NMR

[0469] Proton NMR spectra are collected using a suitable instrument, such as a 500 MHz Varian pulsed Fourier transform NMR spectrometer equipped with a variable temperature proton detection probe operating at 120 °C. A typical measurement of NMR spectra includes dissolving a polymer sample in 1,1,2,2-tetrachloroethane-d2 ("TCE-d2") and transferring to a 5 mm glass NMR tube. Typical acquisition parameters are a scan width of 10 KHz, a pulse width of 30 degrees, an acquisition time of 2 seconds, an acquisition delay of 5 seconds, and 120 scans. Chemical shifts are measured relative to the TCE-d2 signal set at 5.98 ppm.

[0470] Dynamic Mechanical Thermal Analysis

[0471] Dynamic mechanical thermal analysis ("DMTA") is performed using a solid analyzer instrument RSA-G2 (TA Instruments). The sample is prepared as a small rectangular sample, approximately 19.0 mm long x 5 mm wide x 0.5 mm thick. The polymer sample is molded on a Carver Lab Press or Wabash Press at about 150 °C. The polymer sample is then loaded between tool clamps at both ends into the open oven of the instrument. A small strip of dimensions 50 mm x 2 mm x 0.5 mm is cut from the plate and loaded into the RSA-G2 using the fiber tool. Temperature is controlled with a forced convection oven. Dynamic temperature isotherms are performed at a heating rate of 2 °C / min using a frequency of 1 Hz and a strain of 0.1%. The elastic modulus and viscous modulus (E' and E") are measured as a function of temperature.

[0472] Fourier Transform Infrared Spectroscopy

[0473] The amount of potassium acetate groups in the AVTA-K polymer was roughly estimated using Fourier Transform Infrared (FTIR) spectroscopy. A KOAc standard sample for FTIR analysis was prepared by weighing 1.4 mg of potassium acetate (KOAc) in a finger tube and adding 576.6 mg of potassium bromide (KBr). The KOAc and KBr powders were mixed as follows: the finger tube was spun for a few minutes to thoroughly mix the components, and then the entire contents of the finger tube were emptied into a 1.3 cm diameter KBr die. A vacuum pump was connected to the KBr die using a rubber hose to remove air, and then the KBr pellet was pressed for ~10 minutes with a 10 ton load. The size of the KBr pellet containing KOAc was evaluated with a micrometer, where the diameter of the disc was measured to be 1.3 cm and the thickness was measured to be 1.602 mm, which corresponds to a volume of 0.2126 cm 3 . Using a mass of 1.4 mg (>99% purity and a molecular weight of 98.15 g / mol) and a KBr disc volume of 0.2126 cm 3 , the concentration of 0.0664 M KOAc in the KBr pellet was estimated. From the KOAc concentration in the KBr disc, the molar absorptivity of KOAc was estimated by taking an FTIR spectrum of the disc and measuring the peak absorbance of the C-O stretch at 1,572 cm -1 . Using the peak absorbance of the C-O stretch at 1,572 cm-1 and the molar concentration of KOAc in the KBr disc, the KOAc molar absorptivity ε = 132.5 M -1 cm -1 was calculated. The AVTA-K polymer containing KOAc functional groups was pressed into polymer plaques at a thickness of 85 μm to ~350 μm at 204 °C (400 °F). An FTIR spectrum was obtained from the AVTA-K polymer plaque, where the peak absorbance of the C-O stretch in the polymer and the KOAc molar absorptivity were used to estimate the concentration of KOAc groups using Beer's Law.

[0474]

[0475] The molar ratio of AVTA-KOAc groups to ethylene or propylene monomer in the AVTA-K polymer was calculated as follows: using the KOAc molar concentration determined from the peak absorbance of the C-O stretch and assuming the AVTA-K polymer has an amorphous density of ~0.853 g / cm 3 . The density of the AVTA-K polymer was assumed to be that of polypropylene (0.850 g / cm 3 ) and polyethylene (0.856 g / cm 3average value of the amorphous density of the polymer. The molecular weight of the AVTA-KOAc group is 194.32 g / mol, and the monomer molecular weight of the polymer is determined from the average composition determined by NMR from a control polymer that lacks the AVTA-KOAc functionality. In cases where NMR composition is not available, the molecular weight of the monomer is selected as the primary monomer used to synthesize the AVTA-K polymer. The formula for determining the mole ratio of AVTA-KOAc groups to monomers of the AVTA-K polymer is given below.

[0476]

[0477]

[0478] Using the molecular weight of the AVTA-KOAc group of 194.32 g / mol, a similar relationship can be used to calculate the mass ratio of AVTA-KOAc groups to polymer. The formula for determining the mass ratio is given with the list values below.

[0479]

[0480] Tensile properties

[0481] Tensile properties (ultimate tensile strength, elongation at break, tensile yield, yield elongation) were determined using a RSA-G2 instrument (TA Instruments) using dog bone specimens with dimensions of 5 mm x 5 mm x 0.5 mm.

[0482] Polymer preparation

[0483] In the following examples, Catalyst-1 is (Me2Si(η 5 -2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(η 1 -N t Bu)TiMe2) and was prepared according to US 9,796,795 (Catalyst A). Activator-1 is (tetra(pentafluorophenyl)boron N,N-dimethylanilinium) and was purchased from W.R. Grace and Conn. Activator 2 is (tetra(pentafluoronaphthalen-2-yl)boron N,N-dimethylanilinium) and was purchased from W.R. Grace and Conn. Ethylidene norbornene (ENB), decene, and octadecene were purchased from Sigma Aldrich, degassed by nitrogen sparging, filtered through neutral alumina, and stored over 3A molecular sieves. KO t Bu was purchased from Sigma Aldrich and used as received.

[0484] Preparation of Bis(isobutyl)(7-octene-1-yl)aluminum (AV-1 / 8)

[0485] AV synthesis is described in co-pending U.S. Publication No. 2018 / 0194872, assigned to the assignee of the present application, and incorporated herein by reference. A 1,000 mL round bottom flask was charged with 663 mL of 1,7-octadiene (4,488.8 mmol) and a stir bar under a N2atmosphere. The flask was brought to 60 °C. To the flask was added neat diisobutylaluminum hydride (63.8 g, 448.9 mmol) dropwise (about 3 drops / sec). After the addition was complete, the reaction was stirred for an additional 30 minutes at 60 °C. The excess 1,7-octadiene was distilled off under dynamic vacuum at 55 °C to give the desired product as a colorless liquid. Yield: 108 g. The product AV-1 / 8 formula was assigned as (C4H9) 2.1 Al(C8H 15 ) 0.9 . 1 H NMR (400 MHz, -d6): δ = 5.78 (m, 1H, =CH), 5.01 (m, 2H, =CH2), 1.95 (m, 4H,— CH2), 1.54 (m, 2H, i Bu-CH), 1.34 (m, 6H,— CH2), 1.04 (d, 12H, i Bu-CH3), 0.49 (t, 2H, Al— CH2), 0.27 (d, 4H, i Bu-CH2) ppm.

[0486]

[0487] Preparation of linear alpha-olefin-AV copolymers

[0488] Ethylene (C2H4) and propylene (C3H6) or LAO were copolymerized with AV-1 / 8 (di(isobutyl)(7-octen-1-yl)aluminum) by vinyl addition polymerization using Catalyst 1 (structure shown below). Some samples were prepared without AV-1 / 8 as controls.

[0489]

[0490] Control 1 : A 2 L autoclave reactor was charged with 600 mL of isohexane. To the reactor was added propylene (100 mL) and 25 wt% tri-n-octylaluminum in hexanes (TNOAL, 2 mL, purchased from Sigma Aldrich). The reactor was brought to 65 °C and ethylene was introduced to the reactor (80 psig). At 65 °C, catalyst 1 (5.0 mg) and 20 mL of toluene solution of activator 1, N,N-dimethylanilinium tetra(5-fluorophenyl)borate [PhNMe2H] [B(C6F5)4] (10.9 mg) along with 200 mL of isohexane were injected to initiate polymerization. Immediately after catalyst injection, an additional 20 psig of ethylene was added to maintain a steady state 100 psig ethylene pressure and a temperature of 70 °C. The polymerization was stirred at 650 rpm and terminated 15 minutes after catalyst injection by introducing air. The polymer was washed with methanol (300 mL), isolated by filtration, and vacuum dried at 70 °C for 12 hours. Yield: 43.47 g.

[0491] Example 1 : A 2 L autoclave reactor was charged with 600 mL of isohexane. To the reactor was added propylene (100 mL), AV-1 / 8 (10 mL), and bis(diisobutylaluminum) oxide (DIBALO, 1 mL of a 20 wt% solution in hexanes, purchased from Nouryon). The reactor was brought to 65 °C and ethylene was introduced to the reactor (80 psig). At 65 °C, catalyst 1 (5.0 mg) and 20 mL of toluene solution of activator 1, N,N-dimethylanilinium tetra(5-fluorophenyl)borate [PhNMe2H] [B(C6F5)4] (10.9 mg) along with 200 mL of isohexane were injected to initiate polymerization. Immediately after catalyst injection, an additional 20 psig of ethylene was added to maintain a steady state 100 psig ethylene pressure and a temperature of 70 °C. The polymerization was stirred at 650 rpm and terminated 15 minutes after catalyst injection by introducing 200 psig CO2. The reaction was allowed to stir for an additional 30 minutes. The reaction was cooled to 40 °C and the pressure was released from the vent valve. To the reactor was added a solution of KOtBu (20 g) in methanol (300 mL). The reaction was heated at 70 °C for 30 minutes. The polymer was washed with methanol (300 mL), isolated by filtration, and vacuum dried at 70 °C for 12 hours. Yield: 45.31 g.

[0492] Control 2: A 2 L autoclave reactor was charged with 600 mL of isohexane. To the reactor was added propylene (75 mL) and 25 wt% tri-n-octylaluminum in hexanes (TNOAL, 2 mL, purchased from Sigma Aldrich). The reactor was brought to 65 °C and ethylene was introduced to the reactor (100 psig). At 65 °C, catalyst 1 (5.0 mg) and 20 mL of toluene solution of activator 1, N,N-dimethylanilinium tetra(5-fluorophenyl)borate [PhNMe2H][B(C6F5)4] (10.9 mg) were injected with 200 mL of isohexane to initiate polymerization. Immediately after catalyst injection, an additional 20 psig of ethylene was added to maintain a steady state 120 psig ethylene pressure and a temperature of 70 °C. The polymerization was stirred at 650 rpm and terminated 15 minutes after catalyst injection by introducing air. The polymer was washed with methanol (300 mL), isolated by filtration, stabilized by the addition of approximately 1,000 ppm Irganox 1076, and vacuum dried at 70 °C for 12 hours. Yield: 28 g.

[0493] Example 2: A 2 L autoclave reactor was charged with 600 mL of isohexane. To the reactor was added propylene (75 mL), AV-1 / 8 (3 mL), and bis(diisobutylaluminum) oxide (DIBALO, 1 mL of a 20 wt% solution in hexanes, purchased from Nouryon). The reactor was brought to 65 °C and ethylene was introduced to the reactor (100 psig). At 65 °C, catalyst 1 (5.0 mg) and 20 mL of toluene solution of activator 1, N,N-dimethylanilinium tetra(5-fluorophenyl)borate [PhNMe2H][B(C6F5)4] (10.9 mg) were injected with 200 mL of isohexane to initiate polymerization. Immediately after catalyst injection, an additional 20 psig of ethylene was added to maintain a steady state 120 psig ethylene pressure and a temperature of 70 °C. The polymerization was stirred at 650 rpm and terminated 15 minutes after catalyst injection by introducing 200 psig CO2. The reaction was allowed to stir for an additional 30 minutes. The reaction was cooled to 40 °C and the pressure was released from the vent valve. A solution of KOtBu (20 g) in methanol (300 mL) was added to the reactor. The reaction was heated at 70 °C for 30 minutes. The polymer was washed with methanol (300 mL), isolated by filtration, stabilized by the addition of approximately 1,000 ppm Irganox 1076, and vacuum dried at 70 °C for 12 hours. Yield: 35 g.

[0494] Control 3: A 2 L autoclave reactor was charged with 600 mL of isohexane. To the reactor was added propylene (75 mL), ENB (10 mL), and 25 wt% tri-n-octylaluminum in hexanes (TNOAL, 2 mL, purchased from Sigma Aldrich). The reactor was brought to 65 °C and ethylene was introduced to the reactor (100 psig). At 65 °C, catalyst 1 (5.0 mg) and a 20 mL toluene solution of activator 1, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate [PhNMe2H][B(C6F5)4] (10.9 mg) were injected with 200 mL of isohexane to initiate polymerization. Immediately after catalyst injection, an additional 20 psig of ethylene was added to maintain a steady state 120 psig ethylene pressure and a temperature of 70 °C. The polymerization was stirred at 650 rpm and terminated 15 minutes after catalyst injection by introducing air. The polymer was washed with methanol (300 mL), isolated by filtration, stabilized by the addition of approximately 1,000 ppm Irganox 1076, and vacuum dried at 70 °C for 12 hours. Yield: 49.06 g.

[0495] Example 3: A 2 L autoclave reactor was charged with 600 mL of isohexane. To the reactor was added propylene (75 mL), ENB (10 mL), AV-1 / 8 (3 mL), and bis(diisobutylaluminum) oxide (DIBALO, 1 mL of a 20 wt% solution in hexanes, purchased from Nouryon). The reactor was brought to 65 °C and ethylene was introduced to the reactor (100 psig). At 65 °C, catalyst 1 (5.0 mg) and a 20 mL toluene solution of activator 1, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate [PhNMe2H][B(C6F5)4] (10.9 mg) were injected with 200 mL of isohexane to initiate polymerization. Immediately after catalyst injection, an additional 20 psig of ethylene was added to maintain a steady state 120 psig ethylene pressure and a temperature of 70 °C. The polymerization was stirred at 650 rpm and terminated 15 minutes after catalyst injection by introducing 200 psig CO2. The reaction was allowed to stir for an additional 30 minutes. The reaction was cooled to 40 °C and the pressure was released from the vent valve. A solution of KOtBu (20 g) in methanol (300 mL) was added to the reactor. The reaction was heated at 70 °C for 30 minutes. The polymer was washed with methanol (300 mL), isolated by filtration, stabilized by the addition of approximately 1,000 ppm Irganox 1076, and vacuum dried at 70 °C for 12 hours. Yield: 48 g.

[0496]

[0497] Example 4: A 2 L autoclave reactor was charged with 300 mL of isohexane. To the reactor was added decene (75 mL), ENB (10 mL), AV-1 / 8 (3 mL), and bis(diisobutylaluminum) oxide (DIBALO, 1 mL of a 20 wt% solution in hexanes, purchased from Nouryon). The reactor was brought to 65 °C and ethylene was introduced to the reactor (80 psig). A 20 mL toluene solution of catalyst 1 (5.0 mg) and activator 2 [PhNMe2H][B(C10F7)4] (15.7 mg) was injected with 200 mL of isohexane to initiate polymerization at 55 °C. Immediately after catalyst injection, an additional 20 psig of ethylene was added to maintain a steady state 100 psig ethylene pressure and a temperature of 60 °C. The polymerization was stirred at 650 rpm and terminated 15 minutes after catalyst injection by introducing 100 psig CO2. The reaction was allowed to stir for an additional 30 minutes. The reaction was cooled to 40 °C and the pressure was released from the vent valve. A solution of KOtBu (20 g) in methanol (300 mL) was added to the reactor. The reaction was heated at 70 °C for 30 minutes. The polymer was washed with methanol (300 mL), isolated by filtration, stabilized by the addition of approximately 1,000 ppm Irganox 1076, and vacuum dried at 70 °C for 12 hours. Yield: 97 g.

[0498] Example 5: A 2 L autoclave reactor was charged with 300 mL of isohexane. To the reactor was added decene (75 mL), ENB (10 mL), AV-1 / 8 (3 mL), and bis(diisobutylaluminum) oxide (DIBALO, 1 mL of a 20 wt% solution in hexanes, purchased from Nouryon). The reactor was brought to 35 °C and ethylene was introduced to the reactor (100 psig). A 20 mL toluene solution of catalyst 1 (5.0 mg) and activator 2 [PhNMe2H][B(C10F7)4] (15.7 mg) was injected with 200 mL of isohexane to initiate polymerization at 35 °C. Immediately after catalyst injection, an additional 20 psig of ethylene was added to maintain a steady state 120 psig ethylene pressure and a temperature of 40 °C. The polymerization was stirred at 650 rpm and terminated 15 minutes after catalyst injection by introducing 100 psig CO2. The reaction was allowed to stir for an additional 30 minutes. The reaction was cooled to 30 °C and the pressure was released from the vent valve. A solution of KOtBu (20 g) in methanol (300 mL) was added to the reactor. The reaction was heated at 70 °C for 30 minutes. The polymer was washed with methanol (300 mL), isolated by filtration, stabilized by the addition of approximately 1,000 ppm Irganox 1076, and vacuum dried at 70 °C for 12 hours. Yield: 90 g.

[0499]

[0500] Example 6: A 2 L autoclave reactor was charged with 300 mL of isohexane. To the reactor was added decene (75 mL), ENB (10 mL), AV-1 / 8 (3 mL), and bis(diisobutylaluminum) oxide (DIBALO, 1 mL of a 20 wt% solution in hexanes, purchased from Nouryon). The reactor was brought to 75 °C and ethylene was introduced to the reactor (60 psig). A solution of catalyst 1 (5.0 mg) and activator 2 [PhNMe2H][B(C10F7)4] (15.7 mg) in 20 mL of toluene was injected with 200 mL of isohexane to initiate polymerization at 75 °C. Immediately after catalyst injection, an additional 20 psig of ethylene was added to maintain a steady state 80 psig ethylene pressure and temperature of 80 °C. The polymerization was stirred at 650 rpm and terminated 15 minutes after catalyst injection by introducing 100 psig of CO2. The reaction was allowed to stir for an additional 30 minutes. The reaction was cooled to 40 °C and the pressure was released from the vent valve. A solution of KOtBu (20 g) in methanol (300 mL) was added to the reactor. The reaction was heated at 70 °C for 30 minutes. The polymer was washed with methanol (300 mL), isolated by filtration, stabilized by the addition of about 1,000 ppm Irganox 1076, and vacuum dried at 70 °C for 12 hours. Yield: 81.15 g.

[0501]

[0502] Table 1 shows the synthesis conditions for the ethylene-propylene-AVTA and ethylene-propylene-AVTA-ENB copolymers prepared via the procedures described above. Table 2 shows the values for Mw, Mn, PDI, composition, and glass transition temperature (Tg) of the copolymers. The values for Mw, Mn, and PDI were determined by GPC-4D (no GPC data for ionic polymers due to poor solubility). The composition can be measured by NMR (no NMR data for ionic polymers due to poor solubility). The carboxylate group concentration in the ionic polymers was determined by FT-IR. The values for Tg can be determined by DSC (scanning from -90 to 210 °C; 10 °C / min). The results confirm the ability of catalyst 1 to incorporate ethylene, propylene, decene, octadecene, AVTA, and / or ENB in the copolymers. g g

[0503] Table 1. Ethylene-propylene-AVTA and ethylene-propylene-AVTA-ENB synthesis conditions

[0504]

[0505]

[0506] ​​Properties of ethylene-propylene-AVTA-K ionomers

[0507] Figure 1 This is a graph illustrating a comparison of FTIR analyses between an ethylene-propylene-AV-K ionomer (Example 1), an ethylene-propylene copolymer (Control 1), and a potassium acetate standard sample according to at least one embodiment. The FTIR method used to generate this data is as described above. The results show that the ethylene-propylene-AVTA-K ionomer and the potassium acetate standard sample each show a similar FTIR value at approximately 1600 cm⁻¹. -1 The presence of an absorption peak at approximately 1600 cm⁻¹ indicates the presence of carboxylate groups. Conversely, the ethylene-propylene copolymer shows an absorption peak at approximately 1600 cm⁻¹. -1 There is no absorption peak at that location.

[0508] Tensile and hysteresis tests were performed on dog bone specimens made of ethylene-propylene-AVTA-K ionomer (Example 1) and ethylene-propylene copolymer (Control 1). Dog bone specimens measuring 5 mm × 5 mm × 0.5 mm were loaded into an RSA-G2 instrument (TA instruments) using a fixture for membrane geometry. The measurement temperature was equilibrated for 5 minutes using a forced convection oven. After temperature equilibration, the specimens were uniaxially deformed at a rate of 0.1 mm / s. The normal force required for deformation was measured using a force sensor, and converted to an engineering stress value by dividing the measured force by the initial cross-sectional area of ​​the dog bone.

[0509] Figure 2A Stress-strain curves for two samples (Example 1 and Control 1) measured at 25°C are shown. The results indicate that the ethylene-propylene-AVTA-K ionomer (Example 1) can elastically deform. In this respect, the ethylene-propylene-AVTA-K ionomer exhibits a maximum elastic range of approximately 460% strain when measured according to ASTM D638. The ethylene-propylene-AVTA-K ionomer exhibits approximately 570% fracture strain when measured according to ASTM D638. In contrast, the ethylene-propylene copolymer only plastically deforms. The ethylene-propylene-AVTA-K ionomer has a tensile strength of approximately 2.5 MPa. The ethylene-propylene-AVTA-K ionomer has a Young's modulus of approximately 5.6 MPa.

[0510] Figure 2B This is a diagram illustrating the hysteresis test of an ethylene-propylene-AVTA-K ionomer (Example 1) measured at 25°C according to at least one embodiment. The results show that the ethylene-propylene-AVTA-K ionomer has approximately 45% tensile residual deformation at 200% deformation.

[0511] Figure 3is a graphical illustration of a comparison of scattering data between ethylene-propylene-AVTA-K ionomer (Example 1) and ethylene-propylene copolymer (Control 1). The results show that the ethylene-propylene-AVTA-K ionomer has a peak at about which indicates the presence of ionic clusters. Thus, the ion exchange reaction results in the formation of an ionomer with local ionic clusters. In contrast, the ethylene-propylene copolymer does not have an ionic cluster peak.

[0512] Figure 4 DMTA analysis of ethylene-propylene-AVTA-K ionomer (Example 2) and ethylene-propylene copolymer (Control 2) experimental samples is shown. The results show that the glass transition temperatures (measured as the temperature at the peak in E") of Control 2 and Example 2 are about the same (-53°C and -51.5°C, respectively). The plot also shows that above Tg, both samples show a plateau in the elastic modulus (E') indicating a rubbery elastic response for both samples. However, for Control 2, the elastic modulus drops significantly at T > 70°C indicating a transition to a liquid-like behavior. However, in the case of Example 2, the plateau modulus remains almost constant up to T = 200°C indicating a solid-like behavior due to the physical crosslinking created by the ionic clusters.

[0513] In general, the polyolefin-based ionomers of the present disclosure have improved mechanical properties, such as increased elasticity and increased strain at break, compared to their precursor copolymers that do not contain ionic groups. In some aspects, the polyolefin-based ionomers of the present disclosure have mechanical properties comparable to crosslinked rubbers. The polyolefin-based ionomers of the present disclosure can also flow and can be reprocessed compared to crosslinked rubbers. In some embodiments, unlike their precursor polymers, the polyolefin-based ionomers can behave like physically crosslinked materials, such as crosslinked rubbers, at room temperature and can be reprocessed into new products at higher temperatures. In some embodiments, the polyolefin-based ionomers can behave as well as or better than soft ethylene propylene rubbers.

[0514] Unless otherwise defined, the phrase "consisting essentially of does not exclude the presence of other steps, elements, or materials, whether or not, a reference is made in the specification, as long as these are not essential to the basic and novel characteristic(s) of the disclosure and, furthermore, do not exclude impurities and variations customary in the art with respect to elements and materials used.

[0515] For convenience, only certain ranges of values are explicitly recited herein. However, any lower limit can be combined with any other upper limit to define a range not explicitly recited, and, similarly, any upper limit can be combined with any other lower limit to define a range not explicitly recited. In addition, even if a range is explicitly recited, every point or individual value within the range is also contemplated. Thus, each point or individual value within the range is also individually and specifically disclosed. The upper and lower limits of these deliberately- recited ranges can be independently combined with any of the other ranges explicitly recited or implicitly contemplated.

[0516] All documents described herein are incorporated by reference herein for purposes of all jurisdictions where such practice is allowed. It will be apparent to one of ordinary skill in the art that various modifications and variations can be made to the present disclosure without departing from the spirit or scope of the disclosure. Thus, it is intended that the present disclosure cover modifications and variations of this disclosure provided such modifications and variations come within the scope of the appended claims and their equivalents. It is therefore intended that the present disclosure not be limited to the specific illustrative embodiments disclosed, but that the disclosure be accorded the widest scope consistent with the principles and features disclosed herein. Similarly, the term "comprising" is considered synonymous with the terms "including", "containing", or "comprising" as those terms are used in the art, with the understanding that the descriptions apply to essentially all equivalent elements whether currently known or in existence at the time of the patent specification or in the future discovered. Likewise, the term "comprising" is considered synonymous with the terms "including", "containing", or "comprising" as those terms are used in the art, with the understanding that the descriptions apply to essentially all equivalent elements whether currently known or in existence at the time of the patent specification or in the future discovered. Likewise, whenever a composition, an element or group of elements is denoted as being "comprised" before the transitional term "comprising", "containing" or "including", it is intended to mean that the composition, element or group of elements is an equivalent composition, element or group of elements having the same function, the same effect or the same purpose as that specifically recited in the patent specification.

[0517] While the present disclosure has been described with respect to a number of embodiments and examples, those skilled in the art, having the benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit of the present disclosure.

Claims

1. An ionic polymer comprising: a copolymer comprising: C2-C 60 α-olefin monomer units; non-essential C2-C 60 α-olefin comonomer units; optional diene units, and 0.1 to 20 weight percent of units derived from an aluminum alkyl monomer, based on the weight of the copolymer, wherein the units comprise the formula -R(A - )-, wherein R is an alkyl group containing 2 to 10 carbon atoms, and A - is an anionic group, wherein the anionic group comprises a carboxylate group; and one or more metal cations derived from an alkali metal, wherein the ionic polymer has a glass transition temperature of -60 to 5 °C and a weight average molecular weight (Mw) of 50 to 5,000 kg / mol.

2. The ionic polymer of claim 1, wherein the metal cation comprises Na or K.

3. The ionic polymer of claim 1, wherein the ionic polymer has a tensile strength of 0.1 MPa to 10 MPa at 25 °C; a Young's modulus of 0.5 MPa to 10 MPa at 40 °C, and a glass transition temperature of -100 °C to -10 °C.

4. A method of making an ionic polymer comprising: providing a copolymer comprising: C2-C 60 alpha-olefin monomer units; non-essential C2-C 60 α-olefin comonomer units; non-essential diene units; and 0.1 wt% to 10 wt% of ethylvinyl aluminum (AV) units based on the weight of the copolymer; wherein the copolymer has AV units randomly incorporated within the copolymer chain, a glass transition temperature of -30 °C or less, and a crystallinity of less than 10%; introducing an oxidizing agent to the copolymer to form a copolymer comprising anionic vinyl groups; and introducing one or more metal cations to the copolymer comprising anionic vinyl groups to form the ionic polymer, wherein the one or more metal cations are selected from an alkali metal, wherein the ionic polymer has a tensile strength due to ionic polymer physical crosslinking of greater than 1 MPa, a glass transition temperature of -30 °C or less, and a crystallinity of less than 10%.

5. The method of claim 4, wherein providing the copolymer comprises: said C2-C 60 introduced into a catalyst system comprising an activator and a catalyst compound; and forming the copolymer under reaction conditions.

6. The method of claim 4, wherein the oxidizing agent is selected from CO2.

7. The method of claim 6, wherein the CO2 is introduced at a pressure of 50 psi to 150 psi, wherein introducing the oxidizing agent to the copolymer is conducted at a temperature of 50 °C to 100 °C for a time of 5 minutes to 30 minutes.

8. The method of claim 5, wherein the activating agent comprises N,N- dimethylanilinium tetra(pentafluorophenyl)borate.

9. The method of claim 5, wherein the catalyst system comprises:

10. The method of claim 4, wherein the vinyl aluminum unit has the formula Al(R') 3-v (R) v wherein R is a hydrocarbylene group having 4 to 12 carbon atoms with a vinyl chain end, wherein R' is a hydrocarbyl group having 3 or more carbon atoms, and wherein v is 1 to 3.

11. The method of claim 4, wherein the ethylvinyl aluminum comprises di(isobutyl)(7- octene-1-yl)aluminum.

12. The method of claim 4, wherein the diene is present, and the diene is selected from the group consisting of vinyl norbornene, norbornadiene, 5-ethylidene-2- norbornene, 5-vinyl-2-norbornene, divinylbenzene, dicyclopentadiene, and one or more combinations thereof.

13. The process of claim 5 wherein the catalyst comprises (Me2Si(η 5 -2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1 -yl)(η 1 -N t Bu)TiMe2), and the activator comprises N,N-dimethylanilinium tetra(pentafluorophenyl)borate.

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